Substrate processing apparatus and semiconductor device manufacturing method

ABSTRACT

Disclosed is a method of manufacturing a semiconductor device including: performing a pre-process to a metal film or a GST film by supplying a first processing gas to a substrate, on a surface of which the metal film or the GST film is formed, without supplying a second processing gas; and performing a formation process to the substrate to which the pre-process has been performed such that a film is formed on the metal film or the GST film by executing at least one cycle of alternately (i) supplying the first processing gas, and (ii) supplying the second processing gas that is activated by plasma excitation.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional application of U.S. application Ser. No.13/230,869, filed on Sep. 13, 2011, the entire disclosure of which isincorporated herein by reference. Further, this application claimspriority under 35 USC 119 from Japanese Patent Application No.2010-240067 filed on Oct. 26, 2010 and Japanese Patent Application No.2010-263626 filed on Nov. 26, 2010, the entire disclosures of which areincorporated herein by reference.

BACKGROUND

1. Technical Field

The present invention relates to a substrate processing apparatus and asemiconductor device manufacturing method, and more particularly, to asubstrate processing apparatus and a semiconductor device manufacturingmethod for processing a substrate using plasma.

2. Related Art

A film forming process of depositing a predetermined thin film on asubstrate by the use of a CVD (Chemical Vapor Deposition) method or anALD (Atomic Layer Deposition) method using plasma is known as asemiconductor device manufacturing process (see Japanese PatentApplication Laid-Open (JP-A No. 2003-297818). A CVD method is a methodof depositing a thin film having elements included in source gasmolecules as constituent elements on a substrate by the use of a gasphase of a gaseous raw material and a reaction on a surface. In the CVDmethod, plural types of source gas including plural elementsconstituting a film to be formed are simultaneously supplied to asubstrate to form a film. In the ALD method, plural types of source gasincluding plural elements constituting a film to be formed arealternately supplied to a substrate to form a film. In the CVD method,the substrate can be processed at a low substrate temperature. Thedeposition of a thin film is controlled at an atomic layer level in theALD method. Plasma is used to promote a chemical reaction of a thin filmdeposited by the use of the CVD method or to remove impurities from thethin film. In the ALD method, plasma is used to assist a chemicalreaction of adsorbed film-forming materials.

However, with the gradual finer design rules in manufacturing asemiconductor device, there has been demand to form a film at a lowsubstrate temperature and it is necessary to raise RF power for formingplasma. When the RF power for forming plasma is raised, damage to asubstrate or a film to be formed increases, which is not preferable.

SUMMARY

Amain object of the present invention is to provide a substrateprocessing apparatus and a semiconductor device manufacturing method,which can reduce the damage to a substrate or a film to be formed andcan lower a substrate processing temperature at the time of processing asubstrate using plasma.

According to a first aspect of the present invention, there is provideda substrate processing apparatus including:

a processing chamber in which a substrate is processed;

plural buffer chambers that are partitioned from the processing chamberand that respectively include a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the processing chamber;

a second processing gas supply system that supplies a second processinggas to the plural buffer chambers;

a power source that outputs RF power;

plasma-generating electrodes that activate the second processing gas ineach of the buffer chambers with an application of the RF power from thepower source;

a heating system that heats the substrate; and

a controller that controls the first processing gas supply system, thepower source, the second processing gas supply system, and the heatingsystem to expose the substrate having a metal film formed on a surfacethereof to the first processing gas, and the second processing gas thatis activated in the plural buffer chambers with an application of RFpower to the electrodes and that is supplied from the plural bufferchambers to the processing chamber to form a film on the metal filmwhile heating the substrate to a self-decomposition temperature of thefirst processing gas or lower.

According to a second aspect of the present invention, there is provideda substrate processing apparatus including:

a processing chamber in which a substrate is processed;

one or more buffer chambers that are partitioned from the processingchamber and that includes a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the processing chamber;

a second processing gas supply system that supplies a second processinggas to the one or more buffer chambers;

a power source that outputs RF power;

a plasma-generating electrode that activates the second processing gasin the one or more buffer chambers with an application of the RF powerfrom the power source; and

a controller that controls the first processing gas supply system, thepower source, and the second processing gas supply system to expose thesubstrate having a metal film formed on a surface thereof to the firstprocessing gas and thereafter to expose the substrate to the firstprocessing gas, and the second processing gas that is activated with theapplication of the RF power to the electrode to form a film on the metalfilm.

According to a third aspect of the present invention, there is provideda semiconductor device manufacturing method including:

loading a substrate having a metal film formed on a surface thereof intoa processing chamber;

supplying a first processing gas, and a second processing gas that isnot activated by plasma excitation to the processing chamber from pluralprocessing gas supply systems independent of each other to pre-processthe substrate;

supplying the first processing gas, and the second processing gas thatis activated by the plasma excitation to the processing chamber from theplural processing gas supply systems to form a predetermined film on thepre-processed substrate; and

unloading the substrate having the predetermined film formed thereonfrom the processing chamber.

BRIEF DESCRIPTION OF THE DRAWINGS

An exemplary embodiment of the present invention will be described indetail based on the following figures, wherein:

FIG. 1 is a perspective view schematically illustrating theconfiguration of a substrate processing apparatus suitably used inexemplary embodiments of the invention;

FIG. 2 is a diagram schematically illustrating an example of aprocessing furnace and members accompanied therewith, which are suitablyused in first to third exemplary embodiments of the invention and is aschematic longitudinal sectional view taken along line B-B of FIG. 3, inwhich the schematic longitudinal section of the processing furnace isshown;

FIG. 3 is a schematic transverse sectional view taken along line A-A inthe processing furnace shown in FIG. 2;

FIG. 4 is a block diagram illustrating a controller suitably used in asubstrate processing apparatus according to first to seventh exemplaryembodiments of the invention and members controlled by the controller;

FIG. 5 is a flowchart illustrating a silicon nitride film formingprocess according to a first exemplary embodiment of the invention;

FIG. 6 is a timing diagram illustrating the silicon nitride film formingprocess according to the first exemplary embodiment of the invention;

FIG. 7 is a diagram illustrating the relationship between RF powersupplied and the number of particles generated;

FIG. 8 is a diagram illustrating a typical in-plane particledistribution of a wafer 200;

FIG. 9 is a flowchart illustrating a silicon nitride film formingprocess according to a second exemplary embodiment of the invention;

FIG. 10 is a timing diagram illustrating a pre-processing in the siliconnitride film forming process according to the second exemplaryembodiment of the invention;

FIG. 11 is a flowchart illustrating a silicon nitride film formingprocess according to a third exemplary embodiment of the invention;

FIG. 12 is a schematic transverse sectional view illustrating amodification of the first to third exemplary embodiments of theinvention;

FIG. 13 is a schematic transverse sectional view illustrating anothermodification of the first to third exemplary embodiments of theinvention;

FIG. 14 is a schematic transverse sectional view illustrating stillanother modification of the first to third exemplary embodiments of theinvention;

FIG. 15 is a schematic transverse sectional view for explaining fourthand fifth exemplary embodiments of the invention;

FIG. 16 is a diagram schematically illustrating an example of aprocessing furnace and members accompanied therewith, which are suitablyused in an eighth exemplary embodiment of the invention and is aschematic longitudinal sectional view taken along line E-E of FIG. 17,in which the schematic longitudinal section of the processing furnace isshown;

FIG. 17 is a schematic transverse sectional view taken along line D-D inthe processing furnace shown in FIG. 16;

FIG. 18 is a schematic transverse sectional view for explaining aseventh exemplary embodiment of the invention;

FIG. 19 is a diagram schematically illustrating an example of aprocessing furnace and members accompanied therewith, which are suitablyused in an eighth exemplary embodiment of the invention and is aschematic longitudinal sectional view taken along line B-B of FIG. 20,in which the schematic longitudinal section of the processing furnace isshown;

FIG. 20 is a schematic transverse sectional view taken along line A-A inthe processing furnace shown in FIG. 19;

FIG. 21 is a schematic transverse sectional view illustrating acomparative example;

FIG. 22 is a table illustrating film forming conditions in an example ofthe eighth exemplary embodiment of the invention and a comparativeexample;

FIG. 23 is a table illustrating the relationship between RF power andparticles in an example of the eighth exemplary embodiment of theinvention and a comparative example;

FIG. 24 is a diagram illustrating the relationship between RF power andparticles in an example of the eighth exemplary embodiment of theinvention and a comparative example;

FIG. 25 is a diagram schematically illustrating an example of aprocessing furnace and members accompanied therewith, which are suitablyused in an eighth exemplary embodiment of the invention and is aschematic longitudinal sectional view taken along line B-B of FIG. 26,in which the schematic longitudinal section of the processing furnace isshown;

FIG. 26 is a schematic transverse sectional view taken along line A-A inthe processing furnace shown in FIG. 25;

FIG. 27 is a partially-enlarged schematic perspective view illustratingthe C part of FIG. 26;

FIG. 28 is a partially-enlarged schematic longitudinal sectional viewillustrating the C part of FIG. 26;

FIG. 29 is a block diagram illustrating a controller suitably used in asubstrate processing apparatus according to a ninth exemplaryembodiments of the invention and members controlled by the controller;

FIGS. 30A to 30F are longitudinal sectional views schematicallyillustrating a resist pattern forming method;

FIGS. 31A to 31D are longitudinal sectional views schematicallyillustrating another pattern forming method;

FIG. 32 is a flowchart illustrating a silicon oxide film forming processused to form a pattern;

FIG. 33 is a timing diagram illustrating the silicon oxide film formingprocess used to form the pattern;

FIG. 34 is a schematic transverse sectional view illustrating amodification of the ninth exemplary embodiment of the invention;

FIG. 35 is a schematic transverse sectional view illustrating anothermodification of the ninth exemplary embodiment of the invention;

FIG. 36 is a schematic transverse sectional view illustrating stillanother modification of the ninth exemplary embodiments of theinvention;

FIG. 37 is a partially-enlarged schematic perspective view forexplaining a tenth embodiment of the invention;

FIG. 38 is a partially-enlarged schematic longitudinal sectional viewfor explaining the tenth embodiment of the invention;

FIG. 39 is a partially-enlarged schematic perspective view forexplaining an eleventh embodiment of the invention;

FIG. 40 is a partially-enlarged schematic longitudinal sectional viewfor explaining the eleventh embodiment of the invention;

FIG. 41 is a diagram schematically illustrating an example of aprocessing furnace and members accompanied therewith, which are suitablyused in an twelfth exemplary embodiment of the invention and is aschematic longitudinal sectional view taken along line E-E of FIG. 42,in which the schematic longitudinal section of the processing furnace isshown; and

FIG. 42 is a schematic transverse sectional view taken along line D-D inthe processing furnace shown in FIG. 41.

DETAILED DESCRIPTION

Hereinafter, exemplary embodiments of the invention will be describedwith reference to the accompanying drawings.

First, a substrate processing apparatus suitably used in the exemplaryembodiments of the invention will be described. The substrate processingapparatus is an example of a semiconductor device manufacturingapparatus used to manufacture a semiconductor device.

In the following description, a vertical batch apparatus performing afilm forming process or the like on a substrate is used as an example ofthe substrate processing apparatus. However, the invention is notlimited to the vertical batch apparatus but for example, a single waferapparatus may be used.

Referring to FIG. 1, a cassette 110 housing wafers 200 as an example ofa substrate is used in a substrate processing apparatus 101 and thewafers 200 are formed of a material such as semiconductor silicon. Thesubstrate processing apparatus 101 includes a housing 111 and a cassettestage 114 is disposed in the housing 111. The cassette 110 is loadedonto the cassette stage 114 or is unloaded from the cassette stage 114by the use of an in-process carrier device (not shown).

The cassette 110 is placed on the cassette stage 114 by the use of thein-process carrier device (not shown) in a state in which wafers 200 inthe cassettes 110 hold a vertical posture and a wafer gateway of thecassette 110 is directed upward. The cassette stage 114 is configured tocause the cassette 110 to rotate clockwise to the back of the housing111 and to rotate vertically by 90° so that the wafers 200 in thecassette 110 are changed to a horizontal posture and the wafer gatewayof the cassette 110 faces the back of the housing 111.

A cassette rack 105 is disposed more to the front region thanapproximately the center in the front-rear direction in the housing 111.The cassette rack 105 is configured to house plural cassettes 110 inplural stages and plural columns. The cassette rack 105 is provided witha transfer rack 123 receiving the cassettes 110 to be carried by a wafertransfer mechanism 125.

A preliminary cassette rack 107 is disposed above the cassette stage 114and is configured to preliminarily store the cassettes 110.

A cassette carrier device 118 is disposed between the cassette stage 114and the cassette rack 105. The cassette carrier device 118 includes acassette elevator 118 a elevating with the cassette 110 supported and acassette carrying mechanism 118 b as a carrying mechanism. The cassettecarrier device 118 is configured to carry the cassette 110 among thecassette stage 114, the cassette rack 105, and the preliminary cassetterack 107 by the ganged operation of the cassette elevator 118 a and thecassette carrying mechanism 118 b.

A wafer transfer mechanism 125 is disposed in the back of the cassetterack 105. The wafer transfer mechanism 125 includes a wafer transferdevice 125 a that can rotate or transfer a wafer 200 in the horizontaldirection and a wafer transfer device elevator 125 b that elevates thewafer transfer device 125 a. The wafer transfer device 125 a is providedwith a tweezers 125 c that picks up the wafer 200. The wafer transfermechanism 125 is configured to charge a boat 217 with the wafers 200 orto discharge the wafers 200 from the boat 217 using the tweezers 125 cas a platform of the wafers 200 by the ganged operation of the wafertransfer device 125 a and the wafer transfer device elevator 125 b.

A processing furnace 202 that heats the wafers 200 is disposed on theupside of the rear part of the housing 111 and the lower end of theprocessing furnace 202 is opened or closed by a furnace opening shutter147.

A boat elevator 115 that elevates the boat 217 relative to theprocessing furnace 202 is disposed below the processing furnace 202. Anarm 128 is connected to an elevation platform of the boat elevator 115and a sealing cap 219 is horizontally fixed to the arm 128. The sealingcap 219 is configured to vertically support the boat 217 and to closethe lower end of the processing furnace 202.

The boat 217 includes plural support members and is configured tohorizontally support plural (for example, 50 to 150 sheets of) wafers200 in a state in which the wafers are concentrically arranged in thevertical direction.

A clean unit 134 a that supplies clean air which is a cleaned atmosphereis disposed above the cassette rack 105. The clean unit 134 a includes afeed fan (not shown) and a dust-proof filter (not shown) and isconfigured to cause the clean air to circulate inside the housing 111.

A clean unit 134 b that supplies clean air is disposed at the left endof the housing 111. The clean unit 134 b includes a feed fan (not shown)and a dust-proof filter (not shown) and is configured to cause the cleanair to circulate in the vicinity of the wafer transfer device 125 a, theboat 217, or the like. The clean air circulates in the vicinity of thewafer transfer device 125 a, the boat 217, or the like and is thendischarged from the housing 111.

The main operation of the substrate processing apparatus 101 will bedescribed below.

When a cassette 110 is loaded into the cassette stage 114 by the use ofthe in-process carrier device (not shown), the cassette 110 is placed onthe cassette stage 114 in a state in which the wafers 200 hold avertical posture on the cassette stage 114 and the wafer gateway of thecassette 110 faces the upside. Thereafter, the cassette 110 is made torotate clockwise to the back of the housing 111 and to rotate verticallyby 90° by the cassette stage 114, so that the wafers 200 in the cassette110 are changed to a horizontal posture and the wafer gateway of thecassette 110 faces the back of the housing 111.

Thereafter, the cassette 110 is automatically carried and handed over toa designated rack position of the cassette rack 105 or the preliminarycassette rack 107, is temporarily stored therein, is then transferred tothe transfer rack 123 from the cassette rack 105 or the preliminarycassette rack 107 by the cassette carrier device 118, or is directlycarried to the transfer rack 123.

When the cassette 110 is transferred to the transfer rack 123, a wafer200 is picked up from the cassette 110 via the wafer gateway of thecassette 110 by the use of the tweezers 125 c of the wafer transferdevice 125 a and is charged in the boat 217. The wafer transfer device125 a handing over the wafer 200 to the boat 217 is returned to thecassette 110 and charges the boat 217 with a subsequent wafer 200.

When the boat 217 is charged with a predetermined number of wafers 200,the furnace opening shutter 147 closing the lower end of the processingfurnace 202 is opened to open the lower end of the processing furnace202. Thereafter, the boat 217 supporting the wafers 200 is loaded intothe processing furnace 202 by the elevating operation of the boatelevator 115 and the bottom of the processing furnace 202 is closed bythe sealing cap 219.

After the loading, a desired process is performed on the wafers 200 inthe processing furnace 202. After performing the desired process, thewafers 200 and the cassette 110 are unloaded from the housing 111reversely in the above-mentioned order.

First to Seventh Embodiments

The background of first to seventh exemplary embodiments of theinvention will be described below.

For example, at a low substrate temperature of 650° C. or lower, theformation of an amorphous silicon nitride film on a substrate is carriedout by the use of the ALD method using DCS (DiChloroSilane) andplasma-excited NH₃ (ammonia). The formation of the amorphous siliconnitride film on the substrate using the ALD method is carried out byrepeatedly performing (performing a cyclic process) four steps of a stepof supplying the DCS to the substrate, a step of removing residual gassuch as the DCS, a step of supplying the plasma-excited NH₃, and a stepof removing residual gas such as NH₃. The thickness of the film can becontrolled depending on the number of cyclic processes in the ALDmethod.

With the recent finer design rules of semiconductor devices, at atemperature of 300° C. more or less, it has been tried to form anamorphous silicon nitride film on a metal film formed on the surface ofa substrate through the use of the ALD method using plasma. However,when the amorphous silicon nitride film is formed at such a lowtemperature, there is a problem in that the adhesion between the metalfilm and the amorphous silicon nitride film is poor and the amorphoussilicon nitride film is peeled off.

The present inventors discovered that particles are generated whenforming the amorphous silicon nitride film through the use of the ALDmethod using plasma, and the adhesion between the metal film and theamorphous silicon nitride film is poor and thus the amorphous siliconnitride film is easily peeled off when the number of particles is great.

The present inventors thought that the DCS is easily subjected tochemical adsorption when the substrate temperature is a high temperatureof 400° C. or higher, but the physical adsorption is superior to thechemical adsorption and thus the DCS does not form a combined hand withthe metal film formed on the surface of the substrate well when thesubstrate temperature is lower than 400° C., thereby deteriorating theadhesion.

The first to seventh exemplary embodiments of the invention to bedescribed below are based on such finding or consideration.Particularly, when an amorphous silicon nitride film is formed at a lowtemperature (350° C. or lower) through the use of the ALD method usingplasma, the number of particles generated can be reduced to improve theadhesion, or a pre-process can be performed to improve the adhesionbefore forming the amorphous silicon nitride film through the use of theALD method using plasma.

First Embodiment

A processing furnace 202 according to the first exemplary embodimentused in the substrate processing apparatus 101 will be described belowwith reference to FIGS. 2 and 3.

Referring to FIGS. 2 and 3, the processing furnace 202 is provided witha heater 207 which is a heating device (heating means) heating thewafers 200. The heater 207 includes a heat-insulating member having acylindrical shape having a closed top and plural heater wires and has aunit configuration in which the heater wires are disposed in theheat-insulating member. Inside the heater 207, a quartz reaction tube203 used to process the wafers 200 is disposed to be coaxial with theheater 207.

A sealing cap 219 as a furnace opening lid that can air-tightly closethe lower opening of the reaction tube 203 is disposed below thereaction tube 203. The sealing cap 219 comes in contact with the lowerend of the reaction tube 203 from the lower side in the verticaldirection. The sealing cap 219 is formed of metal such as stainlesssteel in a disc shape. An airtight member (hereinafter, referred to asan O ring) 220 is disposed between an annular flange disposed at an endof the lower opening of the reaction tube 203 and the surface of thesealing cap 219 so as to air-tightly seal a space therebetween. Aprocessing chamber 201 is formed at least by the reaction tube 203 andthe sealing cap 219.

A boat support 218 supporting the boat 217 is disposed on the sealingcap 219. The boat support 218 is formed of a heat-resistant materialsuch as quartz or silicon carbide and serves as a heat-insulatingportion and a support supporting the boat. The boat 217 is disposedupright on the boat support 218. The boat 217 is formed of aheat-resistant material such as quartz or silicon carbide. The boat 217includes a bottom plate 210 fixed to the boat support 218 and a topplate 211 disposed at the top and has a configuration in which pluralpillars 212 are installed between the bottom plate 210 and the top plate211 (see FIG. 1). Plural sheets of wafers 200 are stored in the boat217. The plural sheets of wafers 200 are stacked in plural stages in thetube axis direction of the reaction tube 203 and are supported by thepillars 212 of the boat 217 in a state in which the wafers have ahorizontal posture with a constant gap therebetween and are arranged tobe concentric.

A boat rotating mechanism 267 causing the boat to rotate is disposed onthe side of the sealing cap 219 opposed to the processing chamber 201.The rotation shaft 265 of the boat rotating mechanism 267 is connectedto the boat support 218 via the sealing cap and the boat 217 is made torotate via the boat support 218 by the boat rotating mechanism 267,whereby the wafers 200 rotate.

The sealing cap 219 elevates in the vertical direction by a boatelevator 115 as an elevation mechanism disposed outside the reactiontube 203, whereby the boat 217 can be loaded into and unloaded from theprocessing chamber 201.

In the processing furnace 202, the boat 217 is supported by the boatsupport 218 and is input to the processing chamber 201 in the state inwhich plural sheets of wafers 200 to be processed in a batch are stackedin plural stages in the boat 217, and the wafers 200 input to theprocessing chamber 201 are heated to a predetermined temperature by theheater 207.

Referring to FIGS. 2 and 3, three gas supply pipes 310, 320, and 330supplying a source gas are connected.

Nozzles 410, 420, and 430 are disposed in the processing chamber 201.The nozzles 410, 420, and 430 pass through the lower part of thereaction tube 203. The nozzle 410 is connected to the gas supply pipe310, the nozzle 420 is connected to the gas supply pipe 320, and thenozzle 430 is connected to the gas supply pipe 330.

A mass flow controller 312 which is a flow rate controller, a valve 314which is an on-off valve, a gas reservoir 315, and a valve 313 which isan on-off valve are disposed sequentially from upstream in the gassupply pipe 310.

A downstream end of the gas supply pipe 310 is connected to an end ofthe nozzle 410. The nozzle 410 is disposed in an arc-like space betweenthe inner wall of the reaction tube 203 and the wafers 200 so as to riseup in the stacking direction of the wafers 200 along the inner wall ofthe reaction tube 203 from the lower part to the upper part. The nozzle410 is configured as an L-shaped long nozzle. Plural gas supply holes411 supplying source gas are formed in the side surface of the nozzle410. The gas supply holes 411 are opened to face the center of thereaction tube 203. The gas supply holes 411 are disposed at a constantpitch from the lower part to the upper part with the same or varyingopening area.

The gas reservoir 315 gathering the gas supplied via the gas supply pipe310 is disposed in the middle of the gas supply pipe 310. The gasreservoir 315 is formed, for example, by a gas tank or a spiral pipehaving a larger capacity than the general pipe. By turning on and offthe valve 314 upstream and the valve 313 downstream from the gasreservoir 315, the gas supplied via the gas supply pipe 310 can begathered in the gas reservoir 315 or the gas gathered in the gasreservoir 315 can be supplied to the processing chamber 201.

In the gas supply pipe 310, a vent line 610 and a valve 612 connected toan exhaust pipe 232 to be described later are disposed between the valve314 and the mass flow controller 312.

The gas supply pipe 310, the mass flow controller 312, the valve 314,the gas reservoir 315, the valve 313, the nozzle 410, the vent line 610,and the valve 612 constitute a gas supply system 301.

A carrier gas supply pipe 510 supplying carrier gas (inert gas) isconnected to the gas supply pipe 310 on the downstream side of the valve313. A mass flow controller 512 and a valve 513 are disposed in thecarrier gas supply pipe 510. The carrier gas supply pipe 510, the massflow controller 512, and the valve 513 constitute a carrier gas supplysystem (inert gas supply system) 501.

In the gas supply pipe 310, the flow rate of source gas is adjusted bythe mass flow controller 312 and the source gas is supplied to the gasreservoir 315 and is gathered in the gas reservoir 315, in a state inwhich the valve 313 is turned off and the valve 314 is turned on. When apredetermined amount of source gas is gathered in the gas reservoir 315,the valve 314 is turned off.

When the source gas is not being supplied to the gas reservoir 315, thevalve 314 is turned off and the valve 612 is turned on, whereby thesource gas is made to flow to the vent line 610 via the valve 612.

When supplying the source gas to the processing chamber 201, the valves314 and 513 are turned off and the valve 313 is turned on, whereby thesource gas is supplied to the processing chamber 201 via the gas supplypipe 310 downstream from the valve 313 at a time.

Sequentially from the upstream, a mass flow controller 322 which is aflow rate controller and a vale 323 which is an on-off valve aredisposed in the gas supply pipe 320.

The downstream end of the gas supply pipe 320 is connected to an end ofthe nozzle 420. The nozzle 420 is disposed in a buffer chamber 423 whichis a gas dispersion space (a discharge chamber, a discharge space).Electrode protecting pipes 451 and 452 to be described later aredisposed in the buffer chamber 423. The nozzle 420, the electrodeprotecting pipe 451, and the electrode protecting pipe 452 are disposedin the buffer chamber 423 in this order.

The buffer chamber 423 is formed by the inner wall of the reaction tube203 and a buffer chamber wall 424. The buffer chamber wall 424 isdisposed in the stacking direction of the wafers 200 in the inner wallof the reaction tube 203 extending from the lower part to the upper partin an arc-like space between the inner wall of the reaction tube 203 andthe wafers 200. A gas supply hole 425 supplying gas is formed in thewall of the buffer chamber wall 424 close to the wafers 200. The gassupply hole 425 is disposed between the electrode protecting pipe 451and the electrode protecting pipe 452. The gas supply hole 425 is openedto face the center of the reaction tube 203. The plural gas supply holes425 are disposed over from the lower part to the upper part of thereaction tube 203 and have the same opening area and the same pitch.

The nozzle 420 is disposed at an end of the buffer chamber 423 so as torise up in the stacking direction of the wafers 200 along the inner wallof the reaction tube 203 from the bottom to the top. The nozzle 420 isconfigured as an L-shaped long nozzle. A gas supply hole 421 supplyingsource gas is formed in the side surface of the nozzle 420. The gassupply hole 421 is opened to face the center of the buffer chamber 423.The plural gas supply holes 421 are disposed over from the lower part ofthe reaction tube 203 to the upper part, similarly to the gas supplyholes 425 of the buffer chamber 423. The plural gas supply holes 421 aredisposed with the same opening area at the same pitch from the upstream(the lower part) to the downstream (the upper part) when the pressuredifference between the buffer chamber 423 and the nozzle 420 is small,but the opening area becomes gradually larger or the pitch becomessmaller from the upstream to the downstream when the pressure differenceis large.

In this embodiment, by adjusting the opening area or the opening pitchof the gas supply holes 421 of the nozzles 420 from the upstream to thedownstream as described above, gas having a difference in flow rate butalmost the same flow volume is ejected from the gas supply holes 421.The gas ejected from the gas supply holes 421 is once introduced intothe buffer chamber 423 and the flow rate of the gas is uniformized inthe buffer chamber 423.

That is, the gas ejected into the buffer chamber 423 from the gas supplyholes 421 of the nozzle 420 is alleviated in particle speed of the gasin the buffer chamber 423 and is then ejected into the processingchamber 201 from the gas supply holes 425 of the buffer chamber 423.Accordingly, the gas ejected into the buffer chamber 423 from the gassupply holes 421 of the nozzle 420 is changed to gas having uniform flowvolume and rate when the gas is ejected into the processing chamber 201from the gas supply holes 425 of the buffer chamber 423.

In the gas supply pipe 320, a vent line 620 and a valve 622 connected tothe exhaust pipe 232 to be described later are disposed between thevalve 323 and the mass flow controller 322.

The gas supply pipe 320, the mass flow controller 322, the valve 323,the nozzle 420, the buffer chamber 423, the vent line 620, and the valve622 constitute a gas supply system 302.

A carrier gas supply pipe 520 supplying carrier gas (inert gas) isconnected to the gas supply pipe 320 on the downstream side of the valve323. A mass flow controller 522 and a valve 523 are disposed in thecarrier gas supply pipe 520. The carrier gas supply pipe 520, the massflow controller 522, and the valve 523 constitute a carrier gas supplysystem (inert gas supply system) 502.

In the gas supply pipe 320, the flow rate of source gas is adjusted bythe mass flow controller 322 and the source gas is then supplied.

When the source gas is not being supplied to the processing chamber 201,the valve 323 is turned off and the valve 622 is turned on, whereby thesource gas is made to flow to the vent line 620 via the valve 622.

When supplying the source gas to the processing chamber 201, the valve622 is turned off and the valve 323 is turned on, whereby the source gasis supplied to the gas supply pipe 320 downstream from the valve 323. Onthe other hand, carrier gas is adjusted in flow rate by the mass flowcontroller 522 and is supplied from the carrier gas supply pipe 520 viathe valve 523. The source gas is merged with the carrier gas downstreamfrom the valve 323 and the merged gas is supplied to the processingchamber 201 via the nozzle 420 and the buffer chamber 423.

Sequentially from the upstream, a mass flow controller 332 which is aflow rate controller and a vale 333 which is an on-off valve aredisposed in the gas supply pipe 330.

The downstream end of the gas supply pipe 330 is connected to an end ofthe nozzle 430. The nozzle 430 is disposed in a buffer chamber 433 whichis a gas dispersion space (a discharge chamber, a discharge space).Electrode protecting pipes 461 and 462 to be described later aredisposed in the buffer chamber 433. The nozzle 430, the electrodeprotecting pipe 461, and the electrode protecting pipe 462 are disposedin the buffer chamber 433 in this order.

The buffer chamber 433 is formed by the inner wall of the reaction tube203 and a buffer chamber wall 434. The buffer chamber wall 434 isdisposed in the stacking direction of the wafers 200 in the inner wallof the reaction tube 203 extending from the lower part to the upper partin an arc-like space between the inner wall of the reaction tube 203 andthe wafers 200. A gas supply hole 435 supplying gas is formed in thewall of the buffer chamber wall 434 close to the wafers 200. The gassupply hole 435 is disposed between the electrode protecting pipe 461and the electrode protecting pipe 462. The gas supply hole 435 is openedto face the center of the reaction tube 203. The plural gas supply holes435 are disposed over from the lower part to the upper part of thereaction tube 203 and have the same opening area and the same pitch.

The nozzle 430 is disposed at an end of the buffer chamber 433 so as torise up in the stacking direction of the wafers 200 along the inner wallof the reaction tube 203 from the bottom to the top. The nozzle 430 isconfigured as an L-shaped long nozzle. A gas supply holes 431 supplyingsource gas is formed in the side surface of the nozzle 430. The gassupply hole 431 is opened to face the center of the buffer chamber 433.The plural gas supply holes 431 are disposed over from the lower part ofthe reaction tube 203 to the upper part, similarly to the gas supplyholes 435 of the buffer chamber 433. The plural gas supply holes 431 aredisposed with the same opening area at the same pitch from the upstream(the lower part) to the downstream (the upper part) when the pressuredifference between the buffer chamber 433 and the nozzle 430 is small,but the opening area becomes gradually larger or the pitch becomessmaller from the upstream to the downstream when the pressure differenceis large.

In this embodiment, by adjusting the opening area or the opening pitchof the gas supply holes 431 of the nozzles 430 from the upstream to thedownstream as described above, gas having a difference in flow rate butalmost the same flow volume is ejected from the gas supply holes 431.The gas ejected from the gas supply holes 431 is once introduced intothe buffer chamber 433 and the flow rate of the gas is uniformized inthe buffer chamber 433.

That is, the gas ejected into the buffer chamber 433 from the gas supplyholes 431 of the nozzle 430 is alleviated in particle speed of the gasin the buffer chamber 433 and is then ejected into the processingchamber 201 from the gas supply holes 435 of the buffer chamber 433.Accordingly, the gas ejected into the buffer chamber 433 from the gassupply holes 431 of the nozzle 430 is changed to gas having uniform flowvolume and rate when the gas is ejected into the processing chamber 201from the gas supply holes 435 of the buffer chamber 433.

In the gas supply pipe 330, a vent line 630 and a valve 632 connected tothe exhaust pipe 232 to be described later are disposed between thevalve 333 and the mass flow controller 332.

The gas supply pipe 330, the mass flow controller 332, the valve 333,the nozzle 430, the buffer chamber 433, the vent line 630, and the valve632 constitute a gas supply system 303.

A carrier gas supply pipe 530 supplying carrier gas (inert gas) isconnected to the gas supply pipe 330 on the downstream side of the valve333. A mass flow controller 532 and a valve 533 are disposed in thecarrier gas supply pipe 530. The carrier gas supply pipe 530, the massflow controller 532, and the valve 533 constitute a carrier gas supplysystem (inert gas supply system) 503.

In the gas supply pipe 330, the flow rate of source gas is adjusted bythe mass flow controller 332 and the source gas is then supplied.

When the source gas is not being supplied to the processing chamber 201,the valve 333 is turned off and the valve 632 is turned on, by which thesource gas is made to flow to the vent line 630 via the valve 632.

When supplying the source gas to the processing chamber 201, the valve632 is turned off and the valve 333 is turned on, by which the sourcegas is supplied to the gas supply pipe 330 downstream from the valve333. On the other hand, carrier gas is adjusted in flow rate by the massflow controller 532 and is supplied from the carrier gas supply pipe 530via the valve 533. The source gas is merged with the carrier gasdownstream from the valve 333 and the merged gas is supplied to theprocessing chamber 201 via the nozzle 430 and the buffer chamber 433.

In the buffer chamber 423, a rod-like electrode 471 and a rod-likeelectrode 472 having a long and thin shape are disposed in the stackingdirection of the wafers 200 from the lower part to the upper part of thereaction tube 203. The rod-like electrode 471 and the rod-like electrode472 are disposed in parallel to the nozzle 420. The rod-like electrode471 and the rod-like electrode 472 are covered with electrode protectingpipes 451 and 452 which are protecting pipes protecting the electrodes,respectively, from the upper part to the lower part and are thusprotected. The rod-like electrode 471 is connected to an RF (RadioFrequency) power source 270 via a matching unit 271 and the rod-likeelectrode 472 is connected to an earth 272 which is a referencepotential. As a result, plasma is generated in a plasma generating areabetween the rod-like electrode 471 and the rod-like electrode 472. Therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protecting pipe 452, the bufferchamber 423, and the gas supply holes 425 constitute a first plasmagenerating structure 429. The rod-like electrode 471, the rod-likeelectrode 472, the electrode protecting pipe 451, the electrodeprotecting pipe 452, the matching unit 271, and the RF power source 270constitute a first plasma source as a plasma generator (plasmagenerating unit). The first plasma source serves as an activationmechanism activating gas with plasma. The buffer chamber 423 serves as aplasma generating chamber.

In the buffer chamber 433, a rod-like electrode 481 and a rod-likeelectrode 482 having a long and thin shape are disposed in the stackingdirection of the wafers 200 from the lower part to the upper part of thereaction tube 203. The rod-like electrode 481 and the rod-like electrode482 are disposed in parallel to the nozzle 420. The rod-like electrode481 and the rod-like electrode 482 are covered with electrode protectingpipes 461 and 462 which are protecting pipes protecting the electrodes,respectively, from the upper part to the lower part and are thusprotected. The rod-like electrode 481 is connected to an RF (RadioFrequency) power source 270 via a matching unit 271 and the rod-likeelectrode 482 is connected to an earth 272 which is a referencepotential. As a result, plasma is generated in a plasma generating areabetween the rod-like electrode 481 and the rod-like electrode 482. Therod-like electrode 481, the rod-like electrode 482, the electrodeprotecting pipe 461, the electrode protecting pipe 462, the bufferchamber 433, and the gas supply holes 425 constitute a first plasmagenerating structure 439. The rod-like electrode 481, the rod-likeelectrode 482, the electrode protecting pipe 461, the electrodeprotecting pipe 462, the matching unit 271, and the RF power source 270constitute a second plasma source as a plasma generator (plasmagenerating unit). The second plasma source serves as an activationmechanism activating gas with plasma. The buffer chamber 433 serves as aplasma generating chamber.

The electrode protecting pipe 451 and the electrode protecting pipe 452are inserted into the buffer chamber 423 via through-holes (not shown)formed in the reaction tube 203 at a height position close to the lowerpart of the boat support 218. The electrode protecting pipe 461 and theelectrode protecting pipe 462 are inserted into the buffer chamber 433via through-holes (not shown) formed in the reaction tube 203 at aheight position close to the lower part of the boat support 218.

The electrode protecting pipe 451 and the electrode protecting pipe 452are configured to insert the rod-like electrode 471 and the rod-likeelectrode 472 into the buffer chamber 423 in a state in which they areisolated from the atmosphere of the buffer chamber 423. The electrodeprotecting pipe 461 and the electrode protecting pipe 462 are configuredto insert the rod-like electrode 481 and the rod-like electrode 482 intothe buffer chamber 433 in a state in which they are isolated from theatmosphere of the buffer chamber 433. When the insides of the electrodeprotecting pipes 451, 452, 461, and 462 have the same atmosphere asexternal air (atmospheric air), the rod-like electrodes 471, 472, 481,and 482 inserted into the electrode protecting pipes 451, 452, 461, and462 are oxidized by the heat from the heater 207. Therefore, an inertgas purging mechanism (not shown) charging and purging inert gas such asnitrogen and suppressing the oxygen concentration to be sufficiently lowto prevent the oxidation of the rod-like electrodes 471, 472, 481, and482 is disposed in the electrode protecting pipes 451, 452, 461, and462.

The plasma generated in this embodiment is referred to as remote plasma.The remote plasma means plasma used to transport the plasma generatedbetween the electrodes to the surface of a processing target through theuse of a gas flow or the like to perform a plasma process. In thisembodiment, since two rod-like electrodes 471 and 472 are received inthe buffer chamber 423 and two rod-like electrodes 481 and 482 arereceived in the buffer chamber 433, ions damaging the wafers 200 hardlyleak into the processing chamber 201 other than the buffer chambers 423and 433. An electric field is generated to surround the two rod-likeelectrodes 471 and 472 (that is, to surround the electrode protectingpipes 451 and 452 receiving the two rod-like electrodes 471 and 472,respectively) to generate plasma, and an electric field is generated tosurround the two rod-like electrodes 481 and 482 (that is, to surroundthe electrode protecting pipes 461 and 462 receiving the two rod-likeelectrodes 481 and 482, respectively) to generate plasma. Active speciescontained in the plasma are supplied to the center of the wafers 200from the outer edge of the wafers 200 via the gas supply holes 425 ofthe buffer chamber 423 and the gas supply holes 435 of the bufferchamber 433. As in this embodiment, in a vertical batch apparatus inwhich plural sheets of wafers 200 are stacked in the state in which themain surfaces thereof are parallel to the horizontal plane, since thebuffer chambers 423 and 433 are disposed on the inner wall surface ofthe reaction tube 203, that is, at the positions close to the wafers 200to be processed, the active species can easily reach the surfaces of thewafers 200 without being deactivated.

Referring to FIGS. 2 and 3, an exhaust hole 230 is disposed in the lowerpart of the reaction tube. The exhaust hole 230 is connected to anexhaust pipe 231. The gas supply holes 411 of the nozzle 410 and theexhaust hole 230 are disposed at positions (opposite positions by 180degrees) opposed to each other with the wafers 200 interposedtherebetween. Accordingly, since the source gas supplied from the gassupply holes 411 flows horizontally over the main surfaces of the wafers200 toward the exhaust pipe 231, the source gas can be easily uniformlysupplied to the entire surface of each wafer 200 and thus a uniform filmcan be formed on the wafer 200.

In this embodiment, the first plasma source constituted by the rod-likeelectrode 471, the rod-like electrode 472, the electrode protecting pipe451, the electrode protective pipe 452, the matching unit 271, and theRF power source 270 and the second plasma source constituted by therod-like electrode 481, the rod-like electrode 482, the electrodeprotecting pipe 461, the electrode protective pipe 462, the matchingunit 271, and the RF power source 270 are provided. When only one plasmasource is provided, the input RF power density per unit volume is greatand a lot of particles are generated. However, in this embodiment, sincetwo plasma sources of the first plasma source and the second plasmasource are provided, the RF power supplied to the respective plasmasources can be reduced (by half) to reduce the number of particlesgenerated, compared with the case in which only one plasma source isprovided. Since the RF power supplied to the plasma sources can bereduced, the damage to the wafers 200 or the films formed on the wafers200 can be reduced. Even when the RF power supplied to the plasmasources is reduced, a sufficient amount of plasma to process a substratecan be generated by the two plasma sources, thereby lowering theprocessing temperature of the wafers 200.

Since the first plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the bufferchamber 423, and the gas supply holes 425 and the second plasmagenerating structure 439 constituted by the rod-like electrode 481, therod-like electrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the buffer chamber 433, and the gas supply holes435 are disposed symmetric with respect to a line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the exhaust hole 230 is disposed on the line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200. Since the gas supply holes 411 of thenozzle 410 are also disposed in the line passing through the center ofthe wafers 200 (the center of the reaction tube 203), it is easy tosupply plasma uniformly to the entire surfaces of the wafers 200 fromboth plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the gas supply holes 411, the gas supply holes 425, and the gassupply holes 435 are disposed so that the distance between the gassupply holes 411 of the nozzle 410 and the gas supply holes 425 of thebuffer chamber 423 is equal to the distance between the gas supply holes411 of the nozzle 410 and the gas supply holes 435 of the buffer chamber433, it is possible to form a uniform film on the wafers 200.

Referring to FIGS. 2 and 3 again, the exhaust pipe 231 discharging theatmosphere in the processing chamber 201 is connected to the exhausthole 230 in the lower part of the reaction tube. A pressure sensor 245as a pressure detector (pressure detecting unit) detecting the pressurein the processing chamber 201 and a vacuum pump 246 as a vacuum exhaustdevice via an APC (Auto Pressure Controller) valve 243 as a pressurecontroller (pressure control unit) are connected to the exhaust pipe231, by which the processing chamber 201 is exhausted by vacuum so thatthe pressure in the processing chamber is a predetermined pressure(degree of vacuum). The exhaust pipe 232 downstream from the vacuum pump246 is connected to a waste gas processing device (not shown) or thelike. The APC valve 243 is an on-off valve that can turn on and off itsvalve to perform the vacuum exhaust or the vacuum exhaust stop of theprocessing chamber 201 and that can adjust the valve aperture ratio toadjust the conductance so as to adjust the pressure in the processingchamber 201. The exhaust pipe 231, the APC valve 243, the vacuum pump246, and the pressure sensor 245 constitute an exhaust system.

A temperature sensor 263 as a temperature detector is disposed in thereaction tube 203 and the processing chamber 201 has a desiredtemperature distribution by adjusting supply power to the heater 207 onthe basis of temperature information detected by the temperature sensor263. The temperature sensor 263 is formed in an L shape, is introducedinto the reaction tube 203 through a manifold 209, and is disposed alongthe inner wall of the reaction tube 203.

The boat 271 is disposed at the center of the reaction tube 203. Theboat 217 can be elevated (loaded and unloaded) relative to the reactiontube 203 through the use of the boat elevator 115. When the boat 217 isloaded into the reaction tube 203, the lower end of the reaction tube203 is air-tightly sealed via the O ring 220 by the sealing cap 219. Theboat 217 is supported by the boat support 218. To improve the uniformityof processes, the boat rotating mechanism 267 is driven to rotate theboat 217 supported by the boat support 218.

Referring to FIG. 4, a controller 280 includes a display 288 displayingan operation menu and the like and an operation input unit 290 havingplural keys and receiving various information or an operationinstruction. The controller 280 includes a CPU 281 controlling theoverall operation of the substrate processing apparatus 101, a ROM 282storing various programs including a control program in advance, a RAM283 temporarily storing a variety of data, an HDD 284 storing andholding a variety of data, a display driver 287 controlling the displayof a variety of information on the display 288 and receiving operationinformation from the display 288, an operation input detecting unit 289detecting an operation state on the operation input unit 290, and acommunication interface (I/F) unit 285 transmitting and receiving avariety of information to and from various members such as a temperaturecontroller 291 to be described later, a pressure controller 294 to bedescribed later, the vacuum pump 246, the boat rotating mechanism 267,the boat elevator 115, the mass flow controllers 312, 322, 332, 512,522, and 532, a valve controller 299 to be described later, the cassettestage 114, the cassette carrier device 118, and the wafer transferdevice 125.

The CPU 281, the ROM 282, the RAM 283, the HDD 284, the display driver287, the operation input detecting unit 289, and the communication I/Funit 285 are connected to each other via a system bus 286. Accordingly,the CPU 281 can access the ROM 282, the RAM 283, and the HDD 284, cancontrol the display of a variety of information on the display 288 viathe display driver 287, can grasp the operation information from thedisplay 288, and can control the transmission and reception of a varietyof information to and from various members via the communication I/Funit 285. The CPU 281 can grasp a user's operation state on theoperation input unit 290 via the operation input detecting unit 289.

The temperature controller 291 includes a heater 207, a heating powersource 250 supplying power to the heater 207, a temperature sensor 263,an communication I/F unit 293 transmitting and receiving a variety ofinformation such as set temperature information to and from thecontroller 280, and a heater controller 292 controlling the supply powerfrom the heating power source 250 to the heater 207 on the basis of thereceived set temperature information and the temperature informationfrom the temperature sensor 263. The heater controller 292 is embodiedby a computer. The communication I/F unit 293 of the temperaturecontroller 291 and the communication I/F unit 285 of the controller 280are connected to each other via a cable 751.

The pressure controller 294 includes an APC valve 243, a pressure sensor245, a communication I/F unit 296 transmitting and receiving a varietyof information such as set pressure information and on-off informationof the APC valve 243 to and from the controller 280, and an APC valvecontroller 295 controlling the turning-on and turning-off or theaperture ratio of the APC valve 243 on the basis of the received setpressure information, the on-off information of the APC valve 243, thepressure information from the pressure sensor 245, and the like. The APCvalve controller 295 is also embodied by a computer. The communicationI/F unit 296 of the pressure controller 294 and the communication I/Funit 285 of the controller 280 are connected to each other via a cable752.

The vacuum pump 246, the boat rotating mechanism 267, the boat elevator115, the mass flow controllers 312, 322, 332, 512, 522, and 532, the RFpower source 270, the cassette stage 114, the cassette carrier device118, and the wafer transfer device 125 are connected to thecommunication I/F unit 285 of the controller 280 via cables 753, 754,755, 756, 757, 758, 759, 760, 761, 762, 781, 782, and 783, respectively.

The valve controller 299 includes valves 313, 314, 323, 333, 513, 523,533, 612, 622, and 632 and an electromagnetic valve group 298controlling the supply of air to the valves 313, 314, 323, 333, 513,523, 533, 612, 622, and 632 which are air valves. The electromagneticvalve group 298 includes electromagnetic valves 297 corresponding to thevalves 313, 314, 323, 333, 513, 523, 533, 612, 622, and 632. Theelectromagnetic valve group 298 and the communication I/F unit 285 ofthe controller 280 are connected to each other via a cable 763.

In this way, various members such as the mass flow controllers 312, 322,332, 512, 522, and 532, the valves 313, 314, 323, 333, 513, 523, 533,612, 622, and 632, the APC valve 243, the heating power source 250, thetemperature sensor 263, the pressure sensor 245, the vacuum pump 246,the boat rotating mechanism 267, the boat elevator 115, and the RF powersource 270 are connected to the controller 280. The controller 280performs the posture control of the cassette 110 through the use of thecassette stage 114, the carrying operation control of the cassette 110through the use of the cassette carrier device 118, the transferoperation control of the wafers 200 through the use of the wafertransfer device 125, the flow rate control of the mass flow controllers312, 322, 332, 512, 522, and 532, the on-off operation control of thevalves 313, 314, 323, 333, 513, 523, 533, 612, 622, and 632, the on-offcontrol of the APC valve 243, the pressure control through the use ofthe aperture ratio adjusting operation based on the pressure informationfrom the pressure sensor 245, the temperature control through the use ofthe power supply adjusting operation from the heating power source 250to the heater 207 on the basis of the temperature information from thetemperature sensor 263, the control of the RF power supplied from the RFpower source 270, the start and stop control of the vacuum pump 246, therotation speed control of the boat rotating mechanism 267, the elevationoperation control of the boat elevator 115, and the like.

An example of a semiconductor device manufacturing process ofmanufacturing a large scale integration circuit (LSI) using theabove-mentioned substrate processing apparatus will be described below.In the following description, the operations of the constituent units ofthe substrate processing apparatus are controlled by the controller 280.

The LSI is manufactured by performing a wafer process of processing awafer and then going through an assembly process, a test process, and areliability test process. The wafer process is divided into a substrateprocess of performing processes of oxidation, diffusion, and the like ona silicon wafer and a wiring process of forming wires on the surfacethereof. In the wiring process, a cleaning process, a thermal treatmentprocess, a film forming process, and the like in addition to alithography process are repeatedly performed. In the lithographyprocess, a resist pattern is formed and the underlying layer of thepattern is processed by performing an etching process using the patternas a mask.

An example in which an amorphous silicon nitride film is formed on a GST(GeSbTe) film which is a metal film formed on the surface of the wafer200 in the substrate process or the wiring process by the use of thesubstrate processing apparatus 101 will be described below.

In the CVD method of the CVD method and the ALD method, plural types ofgas containing plural elements constituting a film to be formed aresimultaneously supplied. In the ALD method, plural types of gascontaining plural elements constituting a film to be formed arealternately supplied. By controlling the processing conditions such as asupply flow rate, a supply time, and plasma power at the time of supply,a silicon oxide film (SiO film) or a silicon nitride film (SiN film) isformed. In such a technique, the supply conditions are controlled sothat the composition ratio of a film is a stoichiometric compositionO/Si≈2, for example, when an SiO film is formed and the compositionratio of a film is a stoichiometric composition N/Si≈1.33.

On the other hand, unlike the ALD, the supply condition may becontrolled so that the composition ratio of a film to be formed is apredetermined composition ratio different from the stoichiometriccomposition. That is, the supply condition is controlled so that atleast one element among plural elements constituting the film to beformed is more excessive with respect to the stoichiometric compositionthan the other elements. In this way, the film may be formed whilecontrolling the ratio of plural elements constituting the film to beformed, that is, controlling the composition ratio of the film. Asequence of forming a silicon oxide film having a stoichiometriccomposition by alternately supply plural types of gas containingdifferent types of elements using the ALD method will be describedbelow.

Here, an example in which an amorphous silicon nitride film is formed ona GST (GeSbTe) film which is a metal film formed on a wafer 200 usingsilicon (Si) as a first element, using nitrogen (N) as a second element,using DCS (DiChloroSilane) which is a silicon-containing material as araw material containing the first element, and using NH₃ (ammonia) whichis a nitrogen-containing material as a reactant gas containing thesecond element will be described with reference to FIGS. 5 and 6. FIG. 5is a flowchart illustrating an amorphous silicon nitride filmmanufacturing process. FIG. 6 is a timing diagram illustrating theamorphous silicon nitride film manufacturing process.

First, the heating power source 250 supplying power to the heater 207 iscontrolled to maintain the temperature in the processing chamber 201 ata temperature of 400° C. or lower which is the self-decompositiontemperature of the DCS and more preferably at a temperature of 350° C.or lower, for example, at 300° C.

Thereafter, plural sheets (100 sheets) wafers 200 having the GST filmformed thereon are charged (wafer charging) in the boat 217 (step S201).The wafers 200 have a diameter of 300 mm.

Thereafter, the vacuum pump 246 is started up. The furnace openingshutter 147 (see FIG. 1) is opened. The boat 217 supporting pluralsheets of wafers 200 is elevated by the use of boat elevator 115 and isloaded (boat loading) into the processing chamber 201 (step S202). Inthis state, the sealing cap 219 seals the lower end of the reaction tube203 through the use of the O ring 220. Thereafter, the boat 217 is madeto rotate by the boat driving mechanism 267 to rotate the wafers 200.

Thereafter, the APC valve 243 is turned on to vacuum-suction theprocessing chamber 201 so as to reach a desired pressure (degree ofvacuum) by the use of the vacuum pump 246. When the temperature of thewafer 200 reaches 300° C. and the temperature is stabilized (step S203),the subsequent steps are sequentially performed in the state in whichthe temperature in the processing chamber 201 is maintained at 300° C.

At this time, the pressure in the processing chamber 201 is measured bythe use of the pressure sensor 245 and the aperture ratio of the APCvalve 244 is controlled in a feedback manner on the basis of themeasured pressure (pressure adjustment). The processing chamber 201 isheated by the heater 207 so as to reach a desired temperature. At thistime, the power supply state from the heating power source 250 to theheater 207 is controlled in a feedback manner on the basis of thetemperature information detected by the temperature sensor 263 so thatthe processing chamber 201 is at a desired temperature (temperatureadjustment).

Pre-Process

As a pre-process, N₂ not activated by plasma is supplied and residualgas is then removed.

Supply of N₂ not Activated by Plasma: Step S211

In step S204, N₂ is supplied from the carrier gas supply pipes 501, 502,and 503. The valve 313 is turned off and the valve 513 is turned on, bywhich N₂ is supplied from the carrier gas supply pipe 510. The flow rateof N₂ is adjusted by the use of the mass flow controller 512. The valve323 is turned off and the valve 523 is turned on, by which N₂ issupplied from the carrier gas supply pipe 520. The flow rate of N₂ isadjusted by the use of the mass flow controller 522. The valve 333 isturned off and the valve 533 is turned on, by which N₂ is supplied fromthe carrier gas supply pipe 530. The flow rate of N₂ is adjusted by theuse of the mass flow controller 532. Since the RF power is not appliedbetween the rod-like electrode 471 and the rod-like electrode 472 andbetween the rod-like electrode 481 and the rod-like electrode 482 fromthe RF power source 270, N₂ is supplied in the state in which it is notactivated by plasma.

Removal of Residual Gas: Step S213

In step S213, residual N₂ is removed from the processing chamber 201.The valve 513 of the carrier gas supply pipe 510 is turned off, thevalve 523 of the carrier gas supply pipe 520 is turned off, and thevalve 533 of the carrier gas supply pipe 530 is turned off, by which thesupply of N₂ to the processing chamber 201 is stopped. At this time, theAPC valve 243 of the exhaust pipe 231 is fully opened and the processingchamber 201 is exhausted by the use of the vacuum pump 246 up to 20 Paor less, by which the residual N₂ remaining in the processing chamber201 is removed from the processing chamber 201.

Formation of Amorphous Silicon Nitride Film

A silicon nitride film forming step of forming an amorphous siliconnitride film is performed by supplying DCS gas and NH₃ gas to theprocessing chamber 201. In the silicon nitride film forming step, thefollowing four steps (S231 to S237) are repeatedly performed. In thisembodiment, the silicon nitride film is formed using the ALD method.

Supply of DCS: Step S231

In step S231, DCS is supplied to the processing chamber 201 via the gassupply pipe 310 and the nozzle 410 of the gas supply system 301.

In the state in which the valve 313 is turned off and the valve 314 isturned on, the DCS is adjusted in flow rate by the mass flow controller312, is supplied to the gas reservoir 315, and is gathered in the gasreservoir 315. When a predetermined volume is gathered in the gasreservoir 315, the valve 314 is turned off to trap the DCS in the gasreservoir 315. The DCS is gathered in the gas reservoir 315 so that thepressure is ten times or more the pressure of the processing chamber201, for example, 13000 Pa or more. The apparatus is configured so thatthe conductance between the gas reservoir 315 and the processing chamber201 is 1.5×10⁻³ m³/s or more. In consideration of the ratio of thevolume of the processing chamber 201 and the volume of the gas reservoir315, when the volume of the processing chamber 201 is 100 L, the volumeof the gas reservoir 315 is preferably in the range of 100 to 300 cc andthe volume of the gas reservoir 315 is preferably 1/1000 to 3/1000 timesthe volume of the processing chamber 201 regarding the volume ratio. Inthis embodiment, the volume of the gas reservoir 315 is 180 cc. The stepof gathering the DCS in the gas reservoir 315 can be first performed inthe course of performing the residual gas removing step (step S213) andcan be then performed in the course of performing an NH₃ supply step(step S235) in the second cycle or later.

When the residual gas removing step (step S213) is ended, the APC valve243 is turned off to stop the exhausting of the processing chamber 201.Thereafter, the valve 313 downstream from the gas reservoir 315 isturned on. Accordingly, the DCS gathered in the gas reservoir 315 issupplied to the processing chamber 201 at a time. At this time, sincethe APC valve 243 of the exhaust pipe 231 is turned off, the pressure ofthe processing chamber 201 rapidly rises up to about 400 to 500 Pa. Thetime for supplying the DCS is set to 2 to 4 seconds and the time forexposing the wafers to the rising pressure atmosphere is set to 2 to 4seconds, so that the total time is set to 6 seconds. The heating powersource 250 supplying power to the heater 207 is controlled to maintainthe inside of the processing chamber 201 at 300° C. When the supply ofDCS to the processing chamber 201 is ended, the valve 313 is turned offand the valve 314 is turned on, by which the supply of DCS to the gasreservoir 315 is started.

At this time, the gas flowing in the processing chamber 201 is only DCSand NH₃ is not present. Accordingly, the DCS does not cause a gas-phasereaction and performs a surface reaction (chemical adsorption) with thesurface of the GST film on the wafer 200 to form a raw material (DCS)adsorbed layer (hereinafter, referred to as an Si-containing layer). Thechemical adsorption layer of DCS includes a discontinuous chemicaladsorption layer as well as a continuous adsorption layer of DCSmolecules.

At the same time, when the valve 523 is turned off to cause N₂ (inertgas) to flow from the carrier gas supply pipe 520 connected to themiddle of the gas supply tube 320, it is possible to prevent the DCS toflow around to the NH₃-side nozzle 420, the buffer chamber 423, or thegas supply pipe 320. Similarly, at the same time, when the valve 533 isturned off to cause N₂ (inert gas) to flow from the carrier gas supplypipe 530 connected to the middle of the gas supply tube 330, it ispossible to prevent the DCS to flow around to the NH₃-side nozzle 430,the buffer chamber 433, or the gas supply pipe 330. Since it is intendedto prevent the DCS from flowing around, the flow rate of N₂ (inert gas)controlled by the mass flow controllers 522 and 532 may be small.

In an ALD apparatus, gas is adsorbed to the surface of an underlyingfilm. The amount of gas adsorbed is proportional to the pressure of thegas and the exposure time to the gas. Therefore, to adsorb a desiredamount of gas for a short time, it is necessary to raise the pressure ofgas for a short time. From this point of view, in this embodiment, sincethe APC valve 243 is turned off and the DCS gathered in the gasreservoir 315 is supplied at a time, it is possible to rapidly raise thepressure of the DCS in the processing chamber 201, therebyinstantaneously adsorbing a desired amount of gas.

Removal of Residual Gas: Step S233

In step S233, the residual gas such as residual DCS is removed from theprocessing chamber 201. The valve 313 of the gas supply pipe 310 isturned off to stop the supply of DCS to the processing chamber 201. Atthis time, the APC valve 243 of the exhaust pipe 231 is fully turned onand the processing chamber 201 is exhausted up to 20 Pa or lower by theuse of the vacuum pump 246 to remove the residual gas such as residualDCS remaining in the processing chamber 201 from the processing chamber201. At this time, when inert gas such as N₂ is supplied to theprocessing chamber 201 from the gas supply pipes 320 and 330, the effectof removing the residual gas such as residual DCS is improved. Theresidual gas removing step (step S233) is performed for about 9 seconds.

Supply of NH₃ Activated by Plasma: Step S235

In step S235, the NH₃ gas is supplied to the buffer chamber 423 from thegas supply pipe 320 of the gas supply system 302 via the gas supplyholes 421 of the nozzle 420 and the NH₃ gas is supplied to the bufferchamber 433 from the gas supply pipe 330 of the gas supply system 303via the gas supply holes 431 of the nozzle 430. At this time, byapplying RF power across the rod-like electrode 471 and the rod-likeelectrode 472 from the RF power source 270 via the matching unit 271,the NH₃ gas supplied to the buffer chamber 423 is excited by plasma, issupplied as active species to the processing chamber 201 via the gassupply holes 425, and is exhausted via the gas exhaust pipe 231. Byapplying RF power across the rod-like electrode 481 and the rod-likeelectrode 482 from the RF power source 270 via the matching unit 271,the NH₃ gas supplied to the buffer chamber 433 is excited by plasma, issupplied as active species to the processing chamber 201 via the gassupply holes 435, and is exhausted via the gas exhaust pipe 231.

NH₃ is adjusted in flow rate by the mass flow controller 322 and issupplied to the buffer chamber 423 from the gas supply pipe 320. NH₃ isadjusted in flow rate by the mass flow controller 332 and is supplied tothe buffer chamber 433 from the gas supply pipe 330. Before NH₃ issupplied to the buffer chamber 423, the valve 323 is turned off and thevalve 622 is turned on, by which NH₃ is made to flow to the vent line620 via the valve 622. Before NH₃ is supplied to the buffer chamber 433,the valve 333 is turned off and the valve 632 is turned on, by which NH₃is made to flow to the vent line 630 via the valve 632. When supplyingNH₃ to the buffer chamber 423, the valve 622 is turned off and the valve323 is turned on, by which NH₃ is supplied to the gas supply pipe 320downstream from the valve 323. At the same time, the valve 523 is turnedon, by which carrier gas (N₂) is supplied from the carrier gas supplypipe 520. The flow rate of the carrier gas (N₂) is adjusted by the massflow controller 522. NH₃ is merged and mixed with the carrier gas (N₂)downstream from the valve 323 and the mixed gas is supplied to thebuffer chamber 423 via the nozzle 420. When supplying NH₃ to the bufferchamber 433, the valve 632 is turned off and the valve 333 is turned on,by which NH₃ is supplied to the gas supply pipe 330 downstream from thevalve 333. At the same time, the valve 533 is turned on, by whichcarrier gas (N₂) is supplied from the carrier gas supply pipe 530. Theflow rate of the carrier gas (N₂) is adjusted by the mass flowcontroller 532. NH₃ is merged and mixed with the carrier gas (N₂)downstream from the valve 333 and the mixed gas is supplied to thebuffer chamber 433 via the nozzle 430.

When the NH₃ gas is excited by plasma and is made to flow as activespecies, the APC valve 243 is appropriately adjusted to set the pressurein the processing chamber 201 to, for example, 40 to 100 Pa. The supplyflow rate of the NH₃ gas controlled by the mass flow controller 322 isset to, for example, 3000 sccm. The flow rate of the NH₃ gas controlledby the mass flow controller 332 is set to, for example, 3000 sccm. Thetime for exposing the wafers 200 to the active species obtained byexciting the NH₃ gas by plasma, that is, the gas supply time, is set to,for example, 23 seconds. The RF power applied across the rod-likeelectrode 471 and the rod-like electrode 472 from the RF power source270 is set to, for example, 50 W. The RF power applied across therod-like electrode 481 and the rod-like electrode 482 from the RF powersource 270 is set to, for example, 50 W. The heating power source 250supplying power to the heater 207 is controlled to maintain theprocessing chamber 201 at 300° C.

When the NH₃ gas is excited by plasma and is made to flow as activespecies and when the APC valve 243 disposed in the exhaust pipe 231 isturned off to stop the vacuum exhaust, there is provided a problem inthat the active species activated by exciting the NH₃ by plasma aredeactivated before reaching the wafers 200 and thus the reaction withthe surface of the wafers 200 is not caused. Accordingly, when the NH₃gas is excited by plasma and is made to flow as active species, the APCvalve 243 is turned on to exhaust the reaction tube 203.

At this time, the gas flowing in the processing chamber 201 is theactive species (NH₃ plasma) obtained by exciting the NH₃ gas by plasmaand the DCS gas is not made to flow in the processing chamber 201.Accordingly, the NH₃ gas does not cause a gas-phase reaction and the NH₃gas changed to active species or activated reacts with asilicon-containing layer as a first layer formed on the GST film on thewafer 200 in step S231. Accordingly, the silicon-containing layer isnitrified and is deformed into a second layer containing silicon (thefirst element) and nitrogen (the second element), that is, a siliconnitride layer.

When the valve 513 is turned on to cause N₂ (inert gas) to flow from thecarrier gas supply pipe 510 connected to the middle of the gas supplypipe 310, it is possible to prevent NH₃ from going around to theDCS-side nozzle 410 or the gas supply pipe 310. Since it is intended toprevent NH₃ from going around, the flow rate of N₂ (inert gas)controlled by the mass flow controller 512 may be small.

When NH₃ is excited by plasma and is supplied as active species, thevalve 314 upstream from the gas reservoir 315 is turned on and the valve313 downstream is turned off, by which the DCS is gathered in the gasreservoir 315. When a predetermined pressure and a predetermined amountof DCS is gathered in the gas reservoir 315, the valve 314 upstream isalso turned off, by which the DCS is trapped in the gas reservoir 315.

Removal of Residual Gas: Step S237

In step S237, the residual gas such as residual NH₃ not reacting orremaining after the oxidation is removed from the processing chamber201. The valve 323 of the gas supply pipe 320 is turned off to stop thesupply of NH₃ to the processing chamber 201, the valve 622 is turned onto cause NH₃ to flow to the vent line 620, the valve 333 of the gassupply pipe 330 is turned off to stop the supply of NH₃ to theprocessing chamber 201, and the valve 632 is turned on to cause NH₃ toflow to the vent line 630. At this time, the APC valve 243 of theexhaust pipe 231 is fully turned on and the processing chamber 201 isexhausted up to 20 Pa or lower by the use of the vacuum pump 246 toremove the residual gas such as residual NH₃ remaining in the processingchamber 201 from the processing chamber 201. At this time, when inertgas such as N₂ is supplied to the processing chamber 201 from the gassupply pipes 320 and 330 which are NH₃ supply lines, the effect ofremoving the residual gas such as residual NH₃ is improved. The residualgas removing step (step S237) is performed for about 5 seconds.

In this embodiment, while the DCS is being gathered in the gas reservoir315, the step of exciting the NH₃ gas by plasma and supplying activespecies (step S235) and the step of removing the residual gas (stepS237) which are steps necessary for the ALD method are performed.Accordingly, any particular step of gathering the DCS is not necessary.

By setting steps S231 to S237 as one cycle and performing at least onecycle (step S239), a silicon nitride film with a predetermined thicknessis formed on the GST film on the wafer 200 by the use of the ALD method.In this embodiment, 500 cycles are performed to form a silicon nitridefilm of 350 Å.

When the film forming process of forming a silicon nitride film with apredetermined thickness is performed, the processing chamber 201 ispurged with inert gas by exhausting the processing chamber 201 whilesupplying inert gas such as N₂ to the processing chamber 201 (gaspurging step: step S241). The gas purging step is preferably carried outby repeatedly performing both the supply of inert gas such as N₂ to theprocessing chamber 201 which is performed by turning off the APC valve243 and turning on the valves 513, 523, and 533 after removing theresidual gas and the vacuum suction of the processing chamber 201 whichis performed by turning off the valves 513, 523, and 533 to stop thesupply of the inert gas such as N₂ to the processing chamber and turningon the APC valve 243.

Thereafter, the boat rotating mechanism 267 is stopped to stop therotation of the boat 217. Thereafter, the valves 513, 523, and 533 areturned on to replace the atmosphere of the processing chamber 201 withthe inert gas such as N₂ (replacement with inert gas) and to return thepressure in the processing chamber 201 to the normal pressure (return toatmospheric pressure: step S243). Thereafter, the sealing cap 219 iselevated down by the boat elevator 115 to open the lower end of thereaction tube 203 and the boat 217 is unloaded to the outside of theprocessing chamber 201 from the lower end of the reaction tube 203 inthe state in which the processed wafers 200 are held in the boat 217(unloading of boat: step S245). Thereafter, the lower end of thereaction tube 203 is closed with the furnace opening shutter 147.Thereafter, the vacuum pump 246 is stopped. Thereafter, the processedwafers 200 are taken out of the boat 217 (discharging of wafer: stepS247). Accordingly, a film forming process (batch process) is ended.

In this embodiment, the plasma generating structure 429 and the plasmagenerating structure 439 are provided and the RF power is distributedand supplied to two plasma generating structures by 50 W. On thecontrary, in the case in which one plasma generating structure isprovided, for example, in the case in which the plasma generatingstructure 439 is not provided and only the plasma generating structure429 is provided, power of 100 W is supplied to the plasma generatingstructure 429. FIG. 7 is a diagram illustrating the relationship betweenthe input RF power (W) and the number of particles generated. In thecase in which only one plasma generating structure is provided, thepower supplied to the plasma generating structure is the same as theinput RF power (W). However, in the case in which two plasma generatingstructures are provided, the power supplied to the respective plasmagenerating structures is half the input RF power (W). Referring to FIG.7, in the case in which two plasma generating structures are provided,it can be seen that the number of particles generated is greatlyreduced, compared with the case in which only one plasma generatingstructure is provided. Accordingly, by providing two plasma generatingstructures, it is possible to greatly reduce the number of particlesgenerated, thereby suppressing or preventing the silicon nitride filmformed on the GST film from being peeled off. FIG. 8 shows a typicalin-plane particle distribution in a wafer 200 in the case in which onlyone plasma generating structure is provided, for example, in the case inwhich the plasma generating structure 439 is not provided but only theplasma generating structure 429 is provided. In consideration of thefact that the particles lean to the peripheral portion of the wafer andthe wafer 200 is processed while rotating, it can be seen that theparticle distribution results from the plasma generating structure 429disposed in the peripheral portion of the wafer 200. On the contrary,when the plasma generating structure 429 and the plasma generatingstructure 439 are provided and the RF power is distributed and suppliedto two plasma generating structures, the particles are not generatedwell.

When the processing temperature is low, there is a need for raising theinput RF power from the viewpoint of maintaining the quality of a formedfilm. On the other hand, when the input RF power is raised, there is aproblem in that the number of particles generated increases, as shown inFIG. 7. As in this embodiment, by providing plural plasma generatingstructure and distributing and supplying the RF power to the pluralplasma generating structures, it is possible to lower the input powerdensity per unit volume of the RF power and thus to reduce the number ofparticles, thereby improving the adhesion.

Second Embodiment

A second embodiment of the invention will be described below withreference to FIGS. 9 and 10.

In the first embodiment, as the pre-process, N₂ not activated by plasmais supplied (step S211) and then the residual gas is removed (stepS213). This embodiment is different from the first embodiment in that atleast one cycle of the supply of DCS (step S221), the removal ofresidual gas (step S223), the supply of NH₃ not excited by plasma (stepS225), and the removal of residual gas (step S227) is performed as apre-process, and is the same as the first embodiment in the otherpoints. The substrate processing apparatus 101 to be used is the sameand the silicon nitride film forming step is also the same.

The supply of DCS (step S221) is the same as the supply of DCS (stepS231) of the first embodiment, the removal of residual gas (step S223)is the same as the removal of residual gas (step S233) of the firstembodiment, and the removal of residual gas (step S227) is the same asthe removal of residual gas (step S237) of the first embodiment. In thesupply of NH₃ excited by plasma (step S235) in the first embodiment, theRF power is applied across the rod-like electrode 471 and the rod-likeelectrode 472 from the RF power source 270 and the RF power is appliedacross the rod-like electrode 481 and the rod-like electrode 482 fromthe RF power source 270. This embodiment is different from the supply ofNH₃ excited by plasma (step S235) in the first embodiment, in that theRF power is not applied across the rod-like electrode 471 and therod-like electrode 472 and across the rod-like electrode 481 and therod-like electrode 482 from the RF power source 270 in the supply of NH₃not excited by plasma (step S225), but is the same in the other points.

Third Embodiment

A third embodiment of the invention will be described below withreference to FIG. 11.

In the first embodiment, as the pre-process, N₂ not activated by plasmais supplied (step S211) and then the residual gas is removed (stepS213). This embodiment is different from the first embodiment, in thatDCS not activated by plasma is supplied (step S215) and then theresidual gas is removed (step S217), but is the same as the firstembodiment in the other points. The substrate processing apparatus 101to be used is the same and the silicon nitride film forming step is alsothe same.

A modification of the first to third embodiments will be described belowwith reference to FIG. 12.

In the first to third embodiments, the first plasma generating structure429 constituted by the rod-like electrode 471, the rod-like electrode472, the electrode protecting pipe 451, the electrode protecting pipe452, the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are symmetric with the line passing through the centerof the wafers 200 (the center of the reaction tube 203), the exhausthole 230 is disposed in the line passing through the centers of thewafers 200 (the center of the reaction tube 203), the gas supply holes411 of the nozzle 410 are disposed in the line passing through thecenters of the wafers 200 (the center of the reaction tube 203), and thefirst plasma generating structure 429 and the second plasma generatingstructure 439 are disposed in the vicinity of the exhaust hole 230. Thismodification is different from the first embodiment, in that the firstplasma generating structure 429 and the second plasma generatingstructure 439 are disposed at the positions (different by 180°) opposedto each other with the wafers 200 interposed therebetween, are disposedsymmetric about the center of the wafer 200 and the center of thereaction tube 203, and the nozzle 410 is disposed between the exhausthole 230 and the second plasma generating structure 439, but is the sameas the first embodiment in the other points.

In this modification, the first plasma source constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided.Therefore, compared with the case in which only one plasma source isprovided, it is possible to lower the input power density per unitvolume of the RF power by distributing and supplying the RF power toplural plasma sources, and thus to reduce the number of particlesgenerated, thereby improving the adhesion. Further, since the RF powersupplied to the plasma sources can be reduced, the damage to the wafers200 or the films formed on the wafers 200 can be reduced. Even when theRF power supplied to the plasma sources is reduced, a sufficient amountof plasma to process a substrate can be generated by the two plasmasources, thereby lowering the processing temperature of the wafers 200.

Since the first plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the bufferchamber 423, and the gas supply holes 425 and the second plasmagenerating structure 439 constituted by the rod-like electrode 481, therod-like electrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the buffer chamber 433, and the gas supply holes435 are disposed at the positions (different by 180°) opposed to eachother with the wafers 200 interposed therebetween and are disposedsymmetric about the center of the wafer 200 and the center of thereaction tube 203, it is easy to supply plasma uniformly to the entiresurfaces of the wafers 200 from both plasma generating structures and itis thus possible to form a uniform film on the wafers 200.

Another modification of the first to third embodiments will be describedbelow with reference to FIG. 13.

In the first embodiment, the first plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protecting pipe 452,the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are symmetric with respect to the line passing throughthe center of the wafers 200 (the center of the reaction tube 203) andthe gas supply holes 411 of the nozzle 410 are disposed in the linepassing through the centers of the wafers 200 (the center of thereaction tube 203). This modification is different from the first tothird embodiments, in that the first plasma generating structure 429 andthe second plasma generating structure 439 are disposed symmetric withrespect to the line passing through the centers of the wafers 200 (thecenter of the reaction tube 203) but the gas supply holes 411 of thenozzle 410 are not disposed in the line passing through the centers ofthe wafers 200 (the center of the reaction tube 203), but is the same asthe first to third embodiments in the other points.

In this modification, the first plasma source constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided.Therefore, compared with the case in which only one plasma source isprovided, it is possible to lower the input power density per unitvolume of the RF power by distributing and supplying the RF power toplural plasma sources, and thus to reduce the number of particlesgenerated, thereby improving the adhesion. Further, since the RF powersupplied to the plasma sources can be reduced, the damage to the wafers200 or the films formed on the wafers 200 can be reduced. Even when theRF power supplied to the plasma sources is reduced, a sufficient amountof plasma to process a substrate can be generated by the two plasmasources, thereby lowering the processing temperature of the wafers 200.

Since the first plasma generating structure constituted by the rod-likeelectrode 471, the rod-like electrode 472, the electrode protecting pipe451, the electrode protective pipe 452, the buffer chamber 423, and thegas supply holes 425 and the second plasma generating structureconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the buffer chamber 433, and the gas supply holes 435 are disposedsymmetric with respect to a line passing through the center of thewafers 200 (the center of the reaction tube 203), it is easy to supplyplasma uniformly to the entire surfaces of the wafers 200 from bothplasma generating structures and it is thus possible to form a uniformfilm on the wafers 200.

Still another modification of the embodiment will be described belowwith reference to FIG. 14.

In this modification, a third plasma generating structure 439′constituted by a rod-like electrode 481′, a rod-like electrode 482′, anelectrode protecting pipe 461′, an electrode protecting pipe 462′, abuffer chamber 433′, and a gas supply holes 435′ and having the samestructure as the second plasma generating structure 439 constituted bythe rod-like electrode 481, the rod-like electrode 482, the electrodeprotecting pipe 461, the electrode protecting pipe 462, the bufferchamber 433, and the gas supply holes 435 is added to the modificationshown in FIG. 13, and the third plasma generating structure 439′ and thefirst plasma generating structure 429 constituted by the rod-likeelectrode 471, the rod-like electrode 472, the electrode protecting pipe451, the electrode protecting pipe 452, the buffer chamber 423, and thegas supply holes 425 are disposed to be symmetric with respect to theline passing through the center of the wafers 200 and the center of thereaction tube 203.

In this modification, the third plasma source constituted by therod-like electrode 481′, the rod-like electrode 482′, the electrodeprotecting pipe 461′, the electrode protective pipe 462′, the matchingunit 271, and the RF power source 270 is added to the first plasmasource constituted by the rod-like electrode 471, the rod-like electrode472, the electrode protecting pipe 451, the electrode protective pipe452, the matching unit 271, and the RF power source 270 and the secondplasma source constituted by the rod-like electrode 481, the rod-likeelectrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the matching unit 271, and the RF power source 270.Therefore, compared with the case in which two plasma sources areprovided, it is possible to still lower the input power density per unitvolume of the RF power by distributing and supplying the RF power to thethree plasma sources, and thus to further reduce the number of particlesgenerated, thereby further improving the adhesion. Further, since the RFpower supplied to the plasma sources can be further reduced, the damageto the wafers 200 or the films formed on the wafers 200 can be furtherreduced. Even when the RF power supplied to the plasma sources isreduced, a sufficient amount of plasma to process a substrate can begenerated by the three plasma sources, thereby lowering the processingtemperature of the wafers 200.

Fourth Embodiment

Referring to FIG. 15, in the second embodiment, the plasma generatingstructure 429 constituted by the rod-like electrode 471, the rod-likeelectrode 472, the electrode protecting pipe 451, the electrodeprotecting pipe 452, the buffer chamber 423, and the gas supply holes425 and the plasma generating structure 439 constituted by the rod-likeelectrode 481, the rod-like electrode 482, the electrode protecting pipe461, the electrode protecting pipe 462, the buffer chamber 433, and thegas supply holes 435 are provided and the gas supply system includes thegas supply system 301 having the gas supply tube 310, the gas supplysystem 302 having the gas supply tube 320, and the gas supply system 303having the gas supply tube 330. This embodiment is different from thesecond embodiment, in that the plasma generating structure 439 is notprovided but only the plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protecting pipe 452, the bufferchamber 423, and the gas supply holes 425 is provided, and the gassupply system 303 is not provided but only the gas supply system 301having the gas supply tube 310 and the gas supply system 302 having thegas supply tube 320 are provided, but is the same in the other points.

In the second embodiment and this embodiment (the fourth embodiment), byperforming at least one cycle of the supply of DCS (step S221), theremoval of residual gas (step S223), the supply of NH₃ not excited byplasma (step S225), and the removal of residual gas (step S227) as thepre-process, it is possible to reduce the number of particles generated,thereby improving the adhesion. As in the second embodiment, theconfiguration having two plasma generating structures has a great effectof reducing the number of particles generated to improve the adhesion.However, in this embodiment including one plasma generating structure,it is also possible to reduce the number of particles generated, therebyimproving the adhesion.

The principle of the pre-process using DCS and NH₃ not activated byplasma is considered as the following. When DCS is supplied to asubstrate in which a metal film such as a GST film is exposed, areaction intermediate of metal and Si with a small thickness is formedon the substrate. At this time, it is considered that Cl contained inthe DCS is also adsorbed to the substrate. When NH₃ is supplied thereto,NH₃ reacts with Si adsorbed to the substrate to form silicide andammonium chloride, by which Cl is removed from the film. At a lowtemperature, NH₃ does not form a silicon nitride film when it is notexcited by plasma. Accordingly, by using NH₃ not activated by plasma,the above-mentioned effect is achieved.

Fifth Embodiment

Referring to FIG. 15, in the third embodiment, the plasma generatingstructure 429 constituted by the rod-like electrode 471, the rod-likeelectrode 472, the electrode protecting pipe 451, the electrodeprotecting pipe 452, the buffer chamber 423, and the gas supply holes425 and the plasma generating structure 439 constituted by the rod-likeelectrode 481, the rod-like electrode 482, the electrode protecting pipe461, the electrode protecting pipe 462, the buffer chamber 433, and thegas supply holes 435 are provided and the gas supply system includes thegas supply system 301 having the gas supply tube 310, the gas supplysystem 302 having the gas supply tube 320, and the gas supply system 303having the gas supply tube 330. This embodiment is different from thethird embodiment, in that the plasma generating structure 439 is notprovided but only the plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protecting pipe 452, the bufferchamber 423, and the gas supply holes 425 is provided, and the gassupply system 303 is not provided but only the gas supply system 301having the gas supply tube 310 and the gas supply system 302 having thegas supply tube 320 are provided, but is the same in the other points.

In the third embodiment and this embodiment (the fifth embodiment), bysupplying DCS not activated by plasma (step S215) and then removing theresidual gas (step S217) as the pre-process, it is possible to reducethe number of particles generated, thereby improving the adhesion. As inthe third embodiment, the configuration having two plasma generatingstructures has a great effect of reducing the number of particlesgenerated to improve the adhesion. However, in this embodiment includingone plasma generating structure, it is also possible to reduce thenumber of particles generated, thereby improving the adhesion.

Sixth Embodiment

A sixth embodiment of the invention will be described below withreference to FIGS. 16 and 17.

In the first to third embodiments, the first plasma generating structure429 constituted by the rod-like electrode 471, the rod-like electrode472, the electrode protecting pipe 451, the electrode protecting pipe452, the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are disposed inside the reaction tube 203. Thisembodiment is different from the first to third embodiments, in that theplasma generating structures are disposed to protrude to the outsidefrom the reaction tube 203, but is the same in the other points.

A long and thin rectangular opening 822 extending from the lower part ofthe reaction tube to the upper part is disposed in the side wall of thereaction tube 203 and a plasma generating chamber wall 428 is disposedon the outer wall of the reaction tube 203 to cover the opening 822. Theplasma generating chamber wall 428 is formed vertically long and thinwith a sectional shape of “⊃”. The plasma generating chamber wall 428 isformed of, for example, quartz. A plasma generating chamber 821 isformed in the plasma generating chamber wall 428. The plasma generatingchamber 821 communicates with the inside of the reaction tube 203 viathe opening 822. The opening 822 extends vertically long and thin from apart lower than the lowest part of the plural wafers 200 stacked andstored in the boat 217 to the upside.

A nozzle 426 is disposed upright at a position (position most apart fromthe center of the reaction tube 203) inside the plasma generatingchamber 821. The lower part of the nozzle 426 is once bent to the insideof the reaction tube 203 and then protrudes to the outside of thereaction tube 203 from the wall of the reaction tube 203 below theplasma generating chamber wall 428, and the end is connected to the gassupply pipe 320.

The nozzle 426 is disposed to rise to the upside in the stackingdirection of the wafers 200 along the inner wall of the reaction tube203 from the lower part to the upper part. The upper end of the nozzle426 is closed. In the side surface of the nozzle 426, plural gas supplyholes 427 supplying gas are disposed in the stacking direction of thewafers 200 from a part lower than the lowest part of the plural wafers200 stacked and stored in the boat 217 to a part upper than the lowestpart. The gas supply holes 427 are opened to face the center of thereaction tube 203. The plural gas supply holes 427 are disposed with thesame opening area and at the same pitch.

A pair of long and thin plasma generating electrodes 473 and 474 opposedto each other is disposed in the vertical direction on the outersurfaces of both side walls 428 a and 428 b of the plasma generatingchamber wall 428. Electrode covers 475 and 476 are disposed to cover theplasma generating electrodes 473 and 474, respectively. An inert gaspurging mechanism charging or purging inert gas such as nitrogen tosuppress the oxygen concentration sufficiently low and to prevent theoxidation of the plasma generating electrodes 473 and 474 is disposed inthe electrode covers 475 and 476.

The plasma generating electrode 473 is connected to the RF power source270 via the matching unit 271 and the plasma generating electrode 474 isconnected to the earth 272 which is a reference potential. The plasmagenerating electrodes 473 and 474, the plasma generating chamber wall428, the plasma generating chamber 821, the opening 822, the nozzle 426,and the gas supply holes 427 constitute a first plasma generatingstructure 820. The plasma generating electrode 473 and 474, the matchingunit 271, and the RF power source 270 constitute a first plasma sourceas a plasma generator (plasma generating unit).

According to this configuration, gas is supplied between the plasmagenerating electrodes 473 and 474 from the gas supply holes 427 of thenozzle 426 disposed inside the plasma generating chamber 821, plasma isgenerated in the plasma generating area between the plasma generatingelectrodes 473 and 474, and the gas diffuses and flows to the center ofthe reaction tube 203 via the opening 822.

A long and thin rectangular opening 832 extending from the lower part ofthe reaction tube to the upper part is disposed in the side wall of thereaction tube 203 and a plasma generating chamber wall 438 is disposedon the outer wall of the reaction tube 203 to cover the opening 832. Theplasma generating chamber wall 438 is formed vertically long and thinwith a sectional shape of “⊃”. The plasma generating chamber wall 438 isformed of, for example, quartz. A plasma generating chamber 831 isformed in the plasma generating chamber wall 438. The plasma generatingchamber 831 communicates with the inside of the reaction tube 203 viathe opening 832. The opening 832 extends vertically long and thin from apart lower than the lowest part of the plural wafers 200 stacked andstored in the boat 217 to the upside.

A nozzle 436 is disposed upright at a position (position most apart fromthe center of the reaction tube 203) inside the plasma generatingchamber 821. The lower part of the nozzle 436 is once bent to the insideof the reaction tube 203 and then protrudes to the outside of thereaction tube 203 from the wall of the reaction tube 203 below theplasma generating chamber wall 438, and the end is connected to the gassupply pipe 330.

The nozzle 436 is disposed to rise to the upside in the stackingdirection of the wafers 200 along the inner wall of the reaction tube203 from the lower part to the upper part. The upper end of the nozzle436 is closed. In the side surface of the nozzle 436, plural gas supplyholes 437 supplying gas are disposed in the stacking direction of thewafers 200 from a part lower than the lowest part of the plural wafers200 stacked and stored in the boat 217 to a part upper than the lowestpart. The gas supply holes 437 are opened to face the center of thereaction tube 203. The plural gas supply holes 437 are disposed with thesame opening area and at the same pitch.

A pair of long and thin plasma generating electrodes 483 and 484 opposedto each other is disposed in the vertical direction on the outersurfaces of both side walls 438 a and 438 b of the plasma generatingchamber wall 438. Electrode covers 485 and 486 are disposed to cover theplasma generating electrodes 483 and 484, respectively. An inert gaspurging mechanism charging or purging inert gas such as nitrogen tosuppress the oxygen concentration sufficiently low and to prevent theoxidation of the plasma generating electrodes 483 and 484 is disposed inthe electrode covers 485 and 486.

The plasma generating electrode 483 is connected to the RF power source270 via the matching unit 271 and the plasma generating electrode 484 isconnected to the earth 272 which is a reference potential. The plasmagenerating electrodes 483 and 484, the plasma generating chamber wall438, the plasma generating chamber 831, the opening 832, the nozzle 436,and the gas supply holes 437 constitute a first plasma generatingstructure 830. The plasma generating electrode 483 and 484, the matchingunit 271, and the RF power source 270 constitute a second plasma sourceas a plasma generator (plasma generating unit).

According to this configuration, gas is supplied between the plasmagenerating electrodes 483 and 484 from the gas supply holes 437 of thenozzle 436 disposed inside the plasma generating chamber 831, plasma isgenerated in the plasma generating area between the plasma generatingelectrodes 483 and 484, and the gas diffuses and flows to the center ofthe reaction tube 203 via the opening 832.

Remote plasma is generated by the plasma generating structures 820 and830 having the above-mentioned configuration. That is, radicalsgenerated in the plasma generating structures 820 and 830 are notdeactivated until reaching the entire surfaces of the wafers 200 in theprocessing chamber 201 and ions generated by the plasma generatingstructures 820 and 830 do not reach the wafers to such an extent todamage the wafers 200 in the processing chamber.

As in this embodiment, when the plasma generating structures 820 and 830are disposed to protrude to the outside of the reaction tube 203, thedistance between the outer peripheries of the wafers 200 and the innerperipheral surface of the reaction tube 203 can be reduced, comparedwith the case in which the buffer chambers 423 and 433 are disposedinside the reaction tube 203 as in the first embodiment.

In this embodiment, the first plasma source constituted by plasmagenerating electrodes 473 and 474, the matching unit 271, and the RFpower source 270 and the second plasma source constituted by the plasmagenerating electrodes 483 and 484, the matching unit 271, and the RFpower source 270 are provided. Therefore, compared with the case inwhich only one plasma source is provided, even when the RF powersupplied to the each plasma source is reduced, a sufficient amount ofplasma to process a substrate can be generated by the two plasmasources, thereby the damage to the wafers 200 or the films formed on thewafers 200 can be reduced, and the processing temperature of the wafers200 can be lowered.

Since the first plasma generating structure 820 constituted by theplasma generating electrodes 473 and 474, the plasma generating chamberwall 428, the plasma generating chamber 821, the opening 822, the nozzle426, and the gas supply holes 427 and the second plasma generatingstructure 830 constituted by the plasma generating electrodes 483 and484, the plasma generating chamber wall 438, the plasma generatingchamber 831, the opening 832, the nozzle 436, and the gas supply holes437 are disposed symmetric with respect to a line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the exhaust hole 230 is disposed on the line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200and it is thus possible to form a uniform film on the wafers 200. Sincethe gas supply holes 411 of the nozzle 410 are also disposed on the linepassing through the center of the wafers 200 (the center of the reactiontube 203), it is easy to supply plasma uniformly to the entire surfacesof the wafers 200 and it is thus possible to form a uniform film on thewafers 200.

In the substrate processing apparatus having the structure according tothis embodiment, the processing method of supplying N₂ not activated byplasma (step S211), removing the residual gas (step S213), and thenforming a silicon nitride film (steps S231 to S237) as a pre-process,which is described with reference to FIG. 5, the processing method ofperforming at least one cycle of the supply of DCS (step S221), theremoval of residual gas (step S223), the supply of NH₃ not excited byplasma (step S225), and the removal of residual gas (step S227) and thenforming a silicon nitride film (steps S231 to S237) as a pre-process,which is described with reference to FIG. 9, or the processing method ofsupplying DCS not activated by plasma (step S215), removing the residualgas (step S217), and then forming a silicon nitride film (steps S231 toS237) as a pre-process, which is described with reference to FIG. 11 canbe used. Accordingly, it is possible to reduce the number of particlesgenerated, thereby improving the adhesion.

Seventh Embodiment

Referring to FIG. 18, the sixth embodiment includes the plasmagenerating structure 820 constituted by the electrodes 473 and 474, theelectrode cover 475, the electrode cover 476, the plasma generatingchamber 821, and the opening 822 and the plasma generating structure 830constituted by the electrode 483, the electrode 484, the electrode cover485, the electrode cover 486, the plasma generating chamber 831, and theopening 832 and the gas supply system includes the gas supply system 301having the gas supply tube 310, the gas supply system 302 having the gassupply tube 320, and the gas supply system 303 having the gas supplytube 330. This embodiment is different from the sixth embodiment, inthat the plasma generating structure 820 is not provided but only theplasma generating structure 830 constituted by the electrode 483, theelectrode 484, the electrode cover 485, the electrode cover 486, theplasma generating chamber 831, and the opening 832 is provided, and thegas supply system 303 is not provided but only the gas supply system 301having the gas supply tube 310 and the gas supply system 302 having thegas supply tube 320 are provided, but is the same in the other points.

In the substrate processing apparatus having the structure according tothis embodiment, the processing method of performing at least one cycleof the supply of DCS (step S221), the removal of residual gas (stepS223), the supply of NH₃ not excited by plasma (step S225), and theremoval of residual gas (step S227) as a pre-process and then forming asilicon nitride film (steps S231 to S237), which is described withreference to FIG. 9, or the processing method of supplying DCS notactivated by plasma (step S215), removing the residual gas (step S217)as a pre-process, and then forming a silicon nitride film (steps S231 toS237), which is described with reference to FIG. 11, can be used.Accordingly, it is possible to reduce the number of particles generated,thereby improving the adhesion.

In the above-mentioned embodiments, the amorphous silicon nitride filmis formed on the GST film, but the embodiments can be applied to a metalfilm other than the GST film. Examples of the metal films which can besuitably employed include Ti, TiN, TiSi, W, WN, WSi, Co, CoSi, Al, AlSi,Cu, and alloys thereof.

Eighth Embodiment

An eighth embodiment of the invention will be described with referenceto FIGS. 19 and 20.

In the above-mentioned embodiments, the processing method of supplyingN₂ not activated by plasma (step S211) and then removing the residualgas (step S213) as a pre-process, which is described with reference toFIG. 5, the processing method of performing at least one cycle of thesupply of DCS (step S221), the removal of residual gas (step S223), thesupply of NH₃ not excited by plasma (step S225), and the removal ofresidual gas (step S227) as a pre-process, which is described withreference to FIG. 9, or the processing method of supplying DCS notactivated by plasma (step S215) and then removing the residual gas (stepS217) as a pre-process, which is described with reference to FIG. 11, isperformed. This embodiment is different from the embodiments, in thatthe pre-process is not performed, but is the same in the other points.The apparatus used in this embodiment is different from the apparatusused in the modifications of the first to third embodiments describedwith reference to FIGS. 2, 4, and 13, in that the gas reservoir 315 andthe valve 314 upstream from the gas reservoir 315 are not used, but isthe same in the other points.

As a comparative example, as shown in FIG. 21, the substrate processingapparatus 101 in which only the plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protecting pipe 452,the buffer chamber 423, and the gas supply holes 425 is provided and thegas supply system does not include the gas supply system 303 butincludes only the gas supply system 304 having the gas supply tube 340and the gas supply system 302 having the gas supply tube 320 is used.

In this comparative example, at a low substrate temperature of about650° C., an amorphous silicon nitride film (hereinafter, abbreviated as“SiN”) is formed by the use of the ALD method using DCS (DiChloroSilane)and NH₃ (ammonia) plasma. The formation of the amorphous silicon nitridefilm on the wafer 200 is carried out by repeatedly performing four stepsof a step of supplying the DCS, a step of removing the DCS, a step ofsupplying the NH₃ plasma, and a step of removing the NH₃. By repeatedlyperforming these four steps, it is possible to deposit an SiN film witha predetermined thickness on the wafer 200. The thickness of the filmcan be controlled depending on the number of cycles in the ALD method.

However, the ALD method using plasma has a problem in that particles canbe easily generated, compared with the method not using plasma. Thisproblem is considered to be based on peeled particle contamination dueto the generation of micro cracks in an accumulated film deposited at aposition other than the wafers 200 as a processing substrate. Theproblem is also a problem with area particles markedly generated whenthe thickness of the continuously-accumulated film increases. When theRF power is raised, the number of particles increases to deteriorate theproblem. The generation of particles is considered to be partially basedon the RF power. With the decrease in size in manufacturing asemiconductor device, the temperature of the wafers 200 tends to belowered. Accordingly, since it is necessary to raise the RF power so asto compensate for the insufficient energy, more particles are generated.

In this embodiment, the first plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protective pipe 452,the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protective pipe 462, the buffer chamber 433, and the gassupply holes 435 are provide, and the first plasma source constituted bythe rod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided.Therefore, the RF power can be dispersed, and compared with the case inwhich only one plasma source is provided, even when the RF powersupplied to each of the plasma sources is reduced, a sufficient amountof plasma to process a substrate can be generated by the two plasmasources, thereby the damage to the wafers 200 or the films formed on thewafers 200 can be reduced and the processing temperature of the wafers200 can be lowered. Further, the generation of the above-mentioned areaparticles can be suppressed.

The number of particles generated is compared under the film formingconditions shown in FIG. 22 by using both the substrate processingapparatus according to this embodiment shown in FIG. 20 and thesubstrate processing apparatus according to the comparative exampleshown in FIG. 21, using a 300 mm wafer as the wafer 200, and setting thetemperature of the wafer 200 to 350° C. The results are on the premisethat the accumulated SiN film thickness of the reaction tube 203 is 1.2μm to 1.3 μm. The values in the X axis of the RF power in FIG. 22 aredescribed in the X axis column of the RF power in FIG. 23. FIG. 23 is atable illustrating the relationship between the RF power and the numberof particles generated with a size of 0.08 μm and FIG. 24 is a graphillustrating the table shown in FIG. 23.

As can be clearly seen from this result, the configuration in which theRF power is distributed and supplied as in this embodiment causes thesmaller number of particles generated even with the same RF power. Asshown in FIG. 14, the configuration in which the RF power is distributedto three parts achieves a superior effect.

Since the most SiN film forming apparatuses using the ALD method areoperated to repeat the film forming process and the gas cleaningprocess, the number of particles generated can be suppressed accordingto this embodiment, thereby elongating the period of the gas cleaning

Ninth Embodiment

A processing furnace 202 according to a ninth embodiment used in thesubstrate processing apparatus 101 will be described below withreference to FIGS. 25 and 26.

The above-mentioned embodiments employ the structure in which the bufferchambers 423, 433, and 433′ or the plasma generating chambers 821 and831 are supplied with O₂ gas to generate plasma of NH₃ (ammonia).However, as long as it is a structure in which plasma is generated usinga buffer chamber or a plasma generating chamber, the film type or thegas type is not particularly limited. For example, a silicon oxide filmmay be formed using BTBAS (SiH₂(NH(C₄H₉)₂, bistertialbutylaminosilane)and O₂. The following embodiment relates to such a case.

In the first embodiment described with reference to FIGS. 2 and 3, sincegas-phase DCS is used in the gas supply system 301, NH₃ is supplied fromthe gas supply systems 302 and 303 using the mass flow controller 312,the gas reservoir 315, and the valve 314 between the gas reservoir 315and the mass flow controller 312. In this embodiment, liquid-phase BTBASis used. Accordingly, this embodiment is different from the firstembodiment, in that a liquid mass flow controller 316, a vaporizer 318,a valve 317 upstream from the liquid mass flow controller 316 are usedinstead of the mass flow controller 312, the gas reservoir 315, and thevalve 314 of the gas supply system 301 and O₂ is supplied from the gassupply systems 302 and 303, but is the same in the other points.

Sequentially from the upstream, a valve 317 which is an on-off valve, aliquid mass flow controller 316 which is a flow rate control unit of aliquid material, a vaporizer 318 which is a vaporization unit(vaporizer), and a valve 313 which is an on-off valve are disposed inthe gas supply pipe 310 of the gas supply system 301.

In the gas supply pipe 310, a vent line 610 and a valve 612 connected tothe exhaust pipe 232 are disposed between the valve 313 and thevaporizer 318.

The gas supply pipe 310, the valve 317, the liquid mass flow controller316, the vaporizer 318, the valve 313, the nozzle 410, the vent line610, and the valve 612 constitute the gas supply system 301.

In the gas supply pipe 310, a liquid material is adjusted in flow rateby the liquid mass flow controller 316, is supplied to the vaporizer318, is vaporized, and is then supplied as source gas.

When the source gas is not being supplied to the processing chamber 201,the valve 313 is turned off and the valve 612 is turned on, by which thesource gas is made to flow to the vent line 610 via the valve 612.

When supplying the source gas to the processing chamber 201, the valve612 is turned off and the valve 313 is turned on, by which the sourcegas is supplied to the gas supply pipe 310 downstream from the valve313. On the other hand, the carrier gas is adjusted in flow rate by themass flow controller 512 and is supplied from the carrier gas supplypipe 510 via the valve 513, the source gas is merged with the carriergas downstream from the valve 313, and the merged gas is supplied to theprocessing chamber 201 via the nozzle 410.

In the buffer chamber 423, a rod-like electrode 471 and a rod-likeelectrode 472 having a long and thin shape are disposed in the stackingdirection of the wafers 200 from the lower part to the upper part of thereaction tube 203. The rod-like electrode 471 and the rod-like electrode472 are covered with electrode protecting pipes 451 and 452 which areprotecting pipes protecting the electrodes, respectively, from the upperpart to the lower part and are thus protected. In the buffer chamber433, a rod-like electrode 481 and a rod-like electrode 482 having a longand thin shape are disposed in the stacking direction of the wafers 200from the lower part to the upper part of the reaction tube 203. Therod-like electrode 481 and the rod-like electrode 482 are covered withelectrode protecting pipes 461 and 462 which are protecting pipesprotecting the electrodes, respectively, from the upper part to thelower part and are thus protected.

Referring to FIGS. 27 and 28, the electrode protecting pipe 461 and theelectrode protecting pipe 462 are inserted into the buffer chamber 423via through-holes 204 and 205 formed in the reaction tube 203 at aheight position close to the lower part of the boat support 218. Theelectrode protecting pipe 461 and the electrode protecting pipe 462 arefixed to the reaction tube 203 at a height position of the through-holes204 and 205. The electrode protecting pipe 461 and the electrodeprotecting pipe 462 are disposed in the buffer chamber 423 to passthrough holes 402 and 403 of an attachment plate 401 and are fixed bythe attachment plate 401. The attachment plate 401 is fixed to thereaction tube 203 and the buffer chamber wall 424. The electrodeprotecting pipe 451 and the electrode protecting pipe 452 have the samestructure as the electrode protecting pipe 461 and the electrodeprotecting pipe 462.

In the present embodiment, the first plasma source constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided. Tolower the processing temperature of the wafer 200 using plasma, it isnecessary to raise the RF power for forming the plasma. However, thedamage to the wafer 200 or the film to be formed increases when the RFpower is raised. On the contrary, this embodiment is provided with twoplasma sources of the first plasma source and the second plasma source.Accordingly, even when the RF power supplied to the plasma sources islow, it is possible to generate a sufficient amount of plasma, comparedwith the case in which only one plasma source is provided. Therefore,when processing the wafer 200 using plasma, it is possible to reduce thedamage to the wafer 200 or the film to be formed and to lower theprocessing temperature of the wafer 200.

Since the first plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the bufferchamber 423, and the gas supply holes 425 and the second plasmagenerating structure 439 constituted by the rod-like electrode 481, therod-like electrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the buffer chamber 433, and the gas supply holes435 are disposed symmetric with respect to a line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the exhaust hole 230 is disposed on the line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200. Since the gas supply holes 411 of thenozzle 410 are also disposed in the line passing through the center ofthe wafers 200 (the center of the reaction tube 203), it is easy tosupply plasma uniformly to the entire surfaces of the wafers 200 fromboth plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the gas supply holes 411, the gas supply holes 425, and the gassupply holes 435 are disposed so that the distance between the gassupply holes 411 of the nozzle 410 and the gas supply holes 425 of thebuffer chamber 423 is equal to the distance between the gas supply holes411 of the nozzle 410 and the gas supply holes 435 of the buffer chamber433, it is possible to form a uniform film on the wafers 200.

Referring to FIG. 29, a controller 280 includes a display 288 displayingan operation menu and the like and an operation input unit 290 havingplural keys and receiving various information or an operationinstruction. The controller 280 includes a CPU 281 controlling theoverall operation of the substrate processing apparatus 101, a ROM 282storing various programs including a control program in advance, a RAM283 temporarily storing a variety of data, an HDD 284 storing andholding a variety of data, a display driver 287 controlling the displayof a variety of information on the display 288 and receiving operationinformation from the display 288, an operation input detecting unit 289detecting an operation state on the operation input unit 290, and acommunication interface (I/F) unit 285 transmitting and receiving avariety of information to and from various members such as a temperaturecontroller 291 to be described later, a pressure controller 294 to bedescribed later, the vacuum pump 246, the boat rotating mechanism 267,the boat elevator 115, the mass flow controllers 312, 322, 332, 512,522, and 532, a valve controller 299 to be described later, the cassettestage 114, the cassette carrier device 118, and the wafer transferdevice 125.

The CPU 281, the ROM 282, the RAM 283, the HDD 284, the display driver287, the operation input detecting unit 289, and the communication I/Funit 285 are connected to each other via a system bus 286. Accordingly,the CPU 281 can access the ROM 282, the RAM 283, and the HDD 284, cancontrol the display of a variety of information on the display 288 viathe display driver 287, can grasp the operation information from thedisplay 288, and can control the transmission and reception of a varietyof information to and from various members via the communication I/Funit 285. The CPU 281 can grasp a user's operation state on theoperation input unit 290 via the operation input detecting unit 289.

The temperature controller 291 includes a heater 207, a heating powersource 250 supplying power to the heater 207, a temperature sensor 263,an communication I/F unit 293 transmitting and receiving a variety ofinformation such as set temperature information to and from thecontroller 280, and a heater controller 292 controlling the supply powerfrom the heating power source 250 to the heater 207 on the basis of thereceived set temperature information and the temperature informationfrom the temperature sensor 263. The heater controller 292 is embodiedby a computer. The communication I/F unit 293 of the temperaturecontroller 291 and the communication I/F unit 285 of the controller 280are connected to each other via a cable 751.

The pressure controller 294 includes an APC valve 243, a pressure sensor245, a communication I/F unit 296 transmitting and receiving a varietyof information such as set pressure information and on-off informationof the APC valve 243 to and from the controller 280, and an APC valvecontroller 295 controlling the turning-on and turning-off or theaperture ratio of the APC valve 243 on the basis of the received setpressure information, the on-off information of the APC valve 243, thepressure information from the pressure sensor 245, and the like. The APCvalve controller 295 is also embodied by a computer. The communicationI/F unit 296 of the pressure controller 294 and the communication I/Funit 285 of the controller 280 are connected to each other via a cable752.

The vacuum pump 246, the boat rotating mechanism 267, the boat elevator115, the liquid mass flow controller 316, the mass flow controllers 322,332, 512, 522, and 532, the RF power source 270, the cassette stage 114,the cassette carrier device 118, and the wafer transfer device 125 areconnected to the communication I/F unit 285 of the controller 280 viacables 753, 754, 755, 756, 757, 758, 759, 760, 761, 762, 781, 782, and783, respectively.

The valve controller 299 includes valves 313, 314, 323, 333, 513, 523,533, 612, 622, and 632 and an electromagnetic valve group 298controlling the supply of air to the valves 313, 314, 323, 333, 513,523, 533, 612, 622, and 632 which are air valves. The electromagneticvalve group 298 includes electromagnetic valves 297 corresponding to thevalves 313, 314, 323, 333, 513, 523, 533, 612, 622, and 632. Theelectromagnetic valve group 298 and the communication I/F unit 285 ofthe controller 280 are connected to each other via a cable 763.

The gas-phase DCS is used in the first embodiment, but the liquid-phaseBTBAS is used in this embodiment. In this embodiment, the liquid massflow controller 316, the vaporizer 318, the valve 317 is used in the gassupply system 301 instead of the mass flow controller 312, the gasreservoir 315, and the valve 314 of the first embodiment. Accordingly,referring to FIG. 6, this embodiment is different from the firstembodiment, in that the liquid mass flow controller 316 is used insteadof the mass flow controller 312 of the first embodiment and the valve317 is used instead of the valve 314, but is the same in the otherpoints.

In this way, various members such as the liquid mass flow controller316, the mass flow controllers 322, 332, 512, 522, and 532, the valves313, 314, 323, 333, 513, 523, 533, 612, 622, and 632, the APC valve 243,the heating power source 250, the temperature sensor 263, the pressuresensor 245, the vacuum pump 246, the boat rotating mechanism 267, theboat elevator 115, and the RF power source 270 are connected to thecontroller 280. The controller 280 performs the flow rate control of theliquid mass flow controller 316, the mass flow controllers 322, 332,512, 522, and 532, the on-off operation control of the valves 313, 314,323, 333, 513, 523, 533, 612, 622, and 632, the on-off control of theAPC valve 243, the pressure control through the use of the apertureratio adjusting operation based on the pressure information from thepressure sensor 245, the temperature control through the use of thepower supply adjusting operation from the heating power source 250 tothe heater 207 on the basis of the temperature information from thetemperature sensor 263, the control of the RF power supplied from the RFpower source 270, the start and stop control of the vacuum pump 246, therotation speed control of the boat rotating mechanism 267, the elevationoperation control of the boat elevator 115, and the like.

An example of a semiconductor device manufacturing process ofmanufacturing a large scale integration circuit (LSI) using theabove-mentioned substrate processing apparatus will be described below.In the following description, the operations of the constituent units ofthe substrate processing apparatus are controlled by the controller 280.

The LSI is manufactured by performing a wafer process of processing awafer and then going through an assembly process, a test process, and areliability test process. The wafer process is divided into a substrateprocess of performing processes of oxidation, diffusion, and the like ona silicon wafer and a wiring process of forming wires on the surfacethereof. In the wiring process, a cleaning process, a thermal treatmentprocess, a film forming process, and the like in addition to alithography process are repeatedly performed. In the lithographyprocess, a resist pattern is formed and the underlying layer of thepattern is processed by performing an etching process using the patternas a mask.

An example of a processing sequence of forming a resist pattern on awafer 200 will be described below with reference to FIGS. 30A to 30F.

In this example, a double pattern technology (DPT) of forming a patternby performing two or more patterning steps is used. According to thisDPT, it is possible to form a pattern finer than a pattern formed by onepatterning step. In the processing sequence, a first resist patternforming step of forming a first resist pattern 705 on a wafer 200, asilicon oxide film forming step of forming a silicon oxide film 706 as afirst resist protecting film on the first resist pattern 705, and asecond resist pattern forming step of forming a second resist pattern709 on the silicon oxide film 706 are performed in this order. The stepswill be described below.

First Resist Pattern Forming Step

In the first resist pattern forming step, the first resist pattern 705is formed on a hard mask 702 formed on the wafer 200. First, a firstresist 703 is applied onto the hard mask 702 formed on the wafer 200(see FIG. 30A).

Then, by performing a baking process, a selective exposure process usinga mask pattern based on a light source such as an ArF excimer lasersource (193 nm) or a KrF excimer laser source (248 nm), a developingprocess, and the like, the first resist pattern 705 is formed (see FIG.30B).

First Resist Protecting Film Forming Step

In the first resist protecting film forming step, a silicon oxide film706 is formed as a protecting film of the first resist pattern 705 onthe first resist pattern 705 formed in the first resist pattern formingstep and on the hard mask 702 in which the first resist pattern 705 isnot formed (see FIG. 30C). Accordingly, it is possible to prevent thevariation in shape or variation in film quality of the first resistpattern 705 and to protect the first resist pattern from the solvent ofa second resist 707. The formation of the silicon oxide film 706 iscarried out using the substrate processing apparatus 101, details ofwhich will be described later.

Second Resist Pattern Forming Step

In the second resist pattern forming step, the second resist pattern 709is formed at a position other than the position at which the firstresist pattern 705 is formed on the silicon oxide film 706 formed on thefirst resist pattern 705 in the first resist protecting film formingstep. In this step, the same process as the first resist pattern formingstep is performed.

First, a second resist 707 is applied onto the silicon oxide film 706which is the protecting film of the first resist pattern 705 (see FIG.30D).

Then, by performing a baking process, a selective exposure process usinga mask pattern based on a light source such as an ArF excimer lasersource (193 nm) or a KrF excimer laser source (248 nm), a developingprocess, and the like, the second resist pattern 709 is formed (see FIG.30E).

As described above, by performing the first resist pattern forming step,the first resist protecting film forming step, and the second resistpattern forming step, it is possible to form a fine resist pattern.

After forming the second resist pattern 709, a first resist protectingfilm removing step described below may be performed to remove thesilicon oxide film 706 as needed after performing predeterminedprocesses (such as size inspection, alignment inspection, and reworking)

First Resist Protecting Film Removing Step

In the first resist protecting film removing step, the silicon oxidefilm 706 as the first resist protecting film formed in the first resistprotecting film forming step is removed (see FIG. 30F).

The removing method is classified into two methods of a wet etchingmethod and a dry etching method. In the case in which the silicon oxidefilm 706 is removed by the wet etching method, examples of the etchantinclude a diluted HF aqueous solution as a hydrofluoric acid (HF)liquid. In the case in which the silicon oxide film 604 is removed bythe dry etching method, for example, oxygen plasma can be used.

The steps of forming a resist pattern two times has been stated above,but the resist pattern may be formed three times or more. In this case,the resist pattern forming step and the silicon oxide film forming stepare repeatedly performed by a predetermined number of times. Theformation of the silicon oxide film is also carried out using thesubstrate processing apparatus 101, details of which will be describedlater.

In the case in which the resist pattern is formed by three or moretimes, the silicon oxide film which is a protecting film may be removedevery time, like the first resist pattern forming step→the first resistprotecting film (first silicon oxide film) forming step→the secondresist pattern forming step→the first resist protecting film (firstsilicon oxide film) removing step→the third resist pattern formingstep→the second resist protecting film (second silicon oxide film)forming step→the fourth resist pattern forming step→the second resistprotecting film (second silicon oxide film) removing step→the fifthresist pattern forming step→ . . . .

It has been described that the first resist pattern 705 is formed on thehard mask 702 formed on the wafer 200, but the hard mask 702 may not beformed. An ACL (Amorphous Carbon Layer) may be used instead of theresist. In the case in which the ACL is used, the processing temperaturefor forming a silicon oxide film protecting the ACL may be higher thanthat of the resist as long as it is equal to or lower than 200° C. Whenthe processing temperature is equal to or lower than 200° C., it ispossible to effectively prevent the reforming of the ACL due to theheating.

Another example of the processing sequence of forming a resist patternon a wafer 200 will be described below with reference to FIGS. 31A to31D.

In this example, a self-aligned double patterning technique (SASP) offorming a fine pattern using a sidewall is used.

First, a resist 721 is formed on a wafer 200 and is patterned using alithography process to form a first resist pattern 722 (see FIG. 31A).

Then, a silicon oxide film 723 is formed on the first resist pattern 722at a low temperature of 200° C. or lower (see FIG. 31B). The formationof the silicon oxide film 723 is carried out using the substrateprocessing apparatus 101, details of which will be described later.

An anisotropic etching process is performed on the silicon oxide film723 by a dry etching method to leave only the silicon oxide film 723 onthe side wall of the resist pattern 722 as a sidewall 724 (see FIG.31C).

Then, the exposed resist 721 is anisotropically etched in the verticaldirection by the use of a dry etching using the sidewall 724 of thesilicon oxide film as a mask to form a fine pattern 725 formed of theresist 721 (see FIG. 31D).

An ACL (Amorphous Carbon Layer) may be used instead of the resist. Inthe case in which the ACL is used, the processing temperature forforming a silicon oxide film protecting the ACL may be higher than thatof the resist as long as it is equal to or lower than 200° C. When theprocessing temperature is equal to or lower than 200° C., it is possibleto effectively prevent the reforming of the ACL due to the heating.

An example in which the silicon oxide film 706 as the first resistprotecting film or the silicon oxide film 723 as the etching mask isformed at a low temperature of 200° C. or lower by the use of thesubstrate processing apparatus 101 will be described.

In the CVD method of the CVD method and the ALD method, plural types ofgas containing plural elements constituting a film to be formed aresimultaneously supplied. In the ALD method, plural types of gascontaining plural elements constituting a film to be formed arealternately supplied. By controlling the processing conditions such as asupply flow rate, a supply time, and plasma power at the time of supply,a silicon oxide film (SiO film) or a silicon nitride film (SiN film) isformed. In such a technique, the supply conditions are controlled sothat the composition ratio of a film is a stoichiometric compositionO/Si≈2, for example, when an SiO film is formed and the compositionratio of a film is a stoichiometric composition N/Si≈1.33.

On the other hand, unlike the ALD, the supply condition may becontrolled so that the composition ratio of a film to be formed is apredetermined composition ratio different from the stoichiometriccomposition. That is, the supply condition is controlled so that atleast one element among plural elements constituting the film to beformed is more excessive with respect to the stoichiometric compositionthan the other elements. In this way, the film may be formed whilecontrolling the ratio of plural elements constituting the film to beformed, that is, controlling the composition ratio of the film. Asequence of forming a silicon oxide film having a stoichiometriccomposition by alternately supply plural types of gas containingdifferent types of elements using the ALD method will be describedbelow.

Here, an example in which a silicon oxide film as an insulating film isformed on a substrate using silicon (Si) as the first element, usingoxygen (O) as the second element, using BTBAS gas, which is obtained byvaporizing a liquid material BTBAS (SiH₂(NH(C₄H₉)₂,bistertialbutylaminosilane), as a silicon-containing material containingthe first element, and using O₂ gas which is an oxygen-containing gas asreaction gas containing the second element will be described withreference to FIGS. 32 to 33. FIG. 32 is a flowchart illustrating asilicon oxide film manufacturing process used to form a pattern. FIG. 33is a timing diagram illustrating the silicon oxide film manufacturingprocess used to form a pattern.

First, the heating power source 250 supplying power to the heater 207 iscontrolled to maintain the temperature in the processing chamber 201 ata temperature of 200° C. or lower and more preferably at a temperatureof 100° C. or lower, for example, at 100° C.

Thereafter, plural wafers 200 having first resist pattern 705 (see FIG.30B) formed thereon or plural wafers 200 having first resist pattern 722(see FIG. 31A) formed thereon are charged (wafer charging) in the boat217 (step S301).

Thereafter, the vacuum pump 246 is started up. The furnace openingshutter 147 (see FIG. 1) is opened. The boat 217 supporting pluralsheets of wafers 200 is elevated by the use of boat elevator 115 and isloaded (boat loading) into the processing chamber 201 (step S302). Inthis state, the sealing cap 219 seals the lower end of the reaction tube203 through the use of the O ring 220. Thereafter, the boat 217 is madeto rotate by the boat driving mechanism 267 to rotate the wafers 200.

Thereafter, the APC valve 243 is turned on to vacuum-suction theprocessing chamber 201 so as to reach a desired pressure (degree ofvacuum) by the use of the vacuum pump 246. When the temperature of thewafer 200 reaches 100° C. and the temperature is stabilized (step S303),the subsequent steps are sequentially performed in the state in whichthe temperature in the processing chamber 201 is maintained at 100° C.

At this time, the pressure in the processing chamber 201 is measured bythe use of the pressure sensor 245 and the aperture ratio of the APCvalve 244 is controlled in a feedback manner on the basis of themeasured pressure (pressure adjustment). The processing chamber 201 isheated by the heater 207 so as to reach a desired temperature. At thistime, the power supply state from the heating power source 250 to theheater 207 is controlled in a feedback manner on the basis of thetemperature information detected by the temperature sensor 263 so thatthe processing chamber 201 is at a desired temperature (temperatureadjustment).

The silicon oxide film forming step of forming the silicon oxide films706 (see FIG. 30C) and 723 (see FIG. 31B) is performed by supplying theBTBAS gas and the O₂ gas to the processing chamber 201. In the siliconoxide film forming step, the following four steps (S304 to S307) aresequentially and repeatedly performed. In this embodiment, the siliconoxide film is formed using the ALD method.

Supply of BTBAS: Step S304

In step S204, the BTBAS gas is supplied to the processing chamber 201via the gas supply pipe 310 of the gas supply system 301 and the nozzle410. The valve 313 is turned off and the valves 317 and 612 are turnedon. The BTBAS is a liquid at the normal temperature, and the liquidBTBAS is adjusted in flow rate by the liquid mass flow controller 316,is supplied to the vaporizer 318, and is vaporized by the vaporizer 318.Before supplying the BTBAS to the processing chamber 201, the valve 313is turned off and the valve 612, by which the BTBAS is made to flow inthe vent line 610 via the valve 612.

When supplying the BTBAS to the processing chamber 201, the valve 612 isturned off and the valve 313 is turned on to supply the BTBAS to the gassupply line 310 downstream from the valve 313, and the valve 513 isturned on to supply carrier gas (N₂) from the carrier gas supply pipe510. The flow rate of the carrier gas (N₂) is adjusted by the mass flowcontroller 512. The BTBAS is merged and mixed with the carrier gas (N₂)downstream from the valve 313, and the mixed gas is supplied to theprocessing chamber 201 via the gas supply holes 411 of the nozzle 410and is discharged via the exhaust pipe 231. At this time, the APC valve243 is appropriately adjusted to maintain the pressure in the processingchamber 201 in the range of 50 to 900 Pa, for example, at 300 Pa. Theflow rate of BTBAS controlled by the liquid mass flow controller 312 isset to the range of 0.05 to 3.00 g/min, for example, 1.00 g/min. Thetime for which the water 200 is exposed to the BTBAS is set to the rangeof 2 to 6 seconds, for example, 3 seconds. The heating power source 250supplying power to the heater 207 is controlled to maintain thetemperature in the processing chamber 201 at a temperature of 200° C. orlower, preferably at a temperature of 100° C. or lower, and for example,at a temperature of 100° C.

At this time, the gas flowing in the processing chamber 201 is onlyBTBAS and N₂ which is inert gas and O₂ is not present. Accordingly, theBTBAS does not cause a gas-phase reaction and performs a surfacereaction (chemical adsorption) with the surface of the wafer 200 of theunderlying film to form a raw material (BTBAS) adsorbed layer(hereinafter, referred to as an Si-containing layer). The chemicaladsorption layer of BTBAS includes a discontinuous chemical adsorptionlayer as well as a continuous adsorption layer of BTBAS molecules.

At the same time, when the valve 523 is turned off to cause N₂ (inertgas) to flow from the carrier gas supply pipe 520 connected to themiddle of the gas supply tube 320, it is possible to prevent the BTBASto flow around to the O₂-side nozzle 420, the buffer chamber 423, or thegas supply pipe 320. Similarly, at the same time, when the valve 533 isturned off to cause N₂ (inert gas) to flow from the carrier gas supplypipe 530 connected to the middle of the gas supply tube 330, it ispossible to prevent the BTBAS to flow around to the O₂-side nozzle 430,the buffer chamber 433, or the gas supply pipe 330. Since it is intendedto prevent the BTBAS from flowing around, the flow rate of N₂ (inertgas) controlled by the mass flow controllers 522 and 532 may be small.

Removal of Residual Gas: Step S305

In step S305, the residual gas such as residual BTBAS is removed fromthe processing chamber 201. The valve 313 of the gas supply pipe 310 isturned off to stop the supply of BTBAS to the processing chamber 201 andthe valve 612 is turned on to cause BTBAS to flow in the vent line 610.At this time, the APC valve 243 of the exhaust pipe 231 is fully turnedon and the processing chamber 201 is exhausted up to 20 Pa or lower bythe use of the vacuum pump 246 to remove the residual gas such asresidual BTBAS remaining in the processing chamber 201 from theprocessing chamber 201. At this time, when inert gas such as N₂ issupplied to the processing chamber 201 from the gas supply pipe 310which is a BTBAS supply line and the gas supply pipes 320 and 330, theeffect of removing the residual gas such as residual BTBAS is improved.

Supply of O₂ Activated by Plasma: Step S306

In step S306, the O₂ gas is supplied to the buffer chamber 423 from thegas supply pipe 320 of the gas supply system 302 via the gas supplyholes 421 of the nozzle 420 and the O₂ gas is supplied to the bufferchamber 433 from the gas supply pipe 330 of the gas supply system 303via the gas supply holes 431 of the nozzle 430. At this time, byapplying RF power across the rod-like electrode 471 and the rod-likeelectrode 472 from the RF power source 270 via the matching unit 271,the O₂ gas supplied to the buffer chamber 423 is excited by plasma, issupplied as active species to the processing chamber 201 via the gassupply holes 425, and is exhausted via the gas exhaust pipe 231. Byapplying RF power across the rod-like electrode 481 and the rod-likeelectrode 482 from the RF power source 270 via the matching unit 271,the O₂ gas supplied to the buffer chamber 433 is excited by plasma, issupplied as active species to the processing chamber 201 via the gassupply holes 435, and is exhausted via the gas exhaust pipe 231.

O₂ is adjusted in flow rate by the mass flow controller 322 and issupplied to the buffer chamber 423 from the gas supply pipe 320. O₂ isadjusted in flow rate by the mass flow controller 332 and is supplied tothe buffer chamber 433 from the gas supply pipe 330. Before O₂ issupplied to the buffer chamber 423, the valve 323 is turned off and thevalve 622 is turned on, by which O₂ is made to flow to the vent line 620via the valve 622. Before O₂ is supplied to the buffer chamber 433, thevalve 333 is turned off and the valve 632 is turned on, by which O₂ ismade to flow to the vent line 630 via the valve 632. When supplying O₂to the buffer chamber 423, the valve 622 is turned off and the valve 323is turned on, by which O₂ is supplied to the gas supply pipe 320downstream from the valve 323. At the same time, the valve 523 is turnedon, by which carrier gas (N₂) is supplied from the carrier gas supplypipe 520. The flow rate of the carrier gas (N₂) is adjusted by the massflow controller 522. O₂ is merged and mixed with the carrier gas (N₂)downstream from the valve 323 and the mixed gas is supplied to thebuffer chamber 423 via the nozzle 420. When supplying O₂ to the bufferchamber 433, the valve 632 is turned off and the valve 333 is turned on,by which O₂ is supplied to the gas supply pipe 330 downstream from thevalve 333. At the same time, the valve 533 is turned on, by whichcarrier gas (N₂) is supplied from the carrier gas supply pipe 530. Theflow rate of the carrier gas (N₂) is adjusted by the mass flowcontroller 532. O₂ is merged and mixed with the carrier gas (N₂)downstream from the valve 333 and the mixed gas is supplied to thebuffer chamber 433 via the nozzle 430.

When the O₂ gas is excited by plasma and is made to flow as activespecies, the APC valve 243 is appropriately adjusted to set the pressurein the processing chamber 201 to a pressure in the range of 50 to 900Pa, for example, 500 Pa. The supply flow rate of the O₂ gas controlledby the mass flow controller 322 is set to a flow rate in the range of2000 to 9000 sccm, for example, 6000 sccm. The flow rate of the O₂ gascontrolled by the mass flow controller 332 is set to a flow rate in therange of 2000 to 9000 sccm, for example, 6000 sccm. The time forexposing the wafers 200 to the active species obtained by exciting theO₂ gas by plasma, that is, the gas supply time, is set to a time in therange of 3 to 20 seconds, for example, 9 seconds. The RF power appliedacross the rod-like electrode 471 and the rod-like electrode 472 fromthe RF power source 270 is set to power in the range of 20 to 600 W, forexample, 200 W. The RF power applied across the rod-like electrode 481and the rod-like electrode 482 from the RF power source 270 is set topower in the range of 20 to 600 W, for example, 200 W. The heating powersource 250 supplying power to the heater 207 is controlled to maintainthe processing chamber 201 at a temperature of 200° C. or lower,preferably at a temperature of 100° C. or lower, and for example, at100°. Since the reaction temperature of the O₂ gas itself is high andthe O₂ gas does not react well at the above-mentioned wafer temperatureand the pressure of the processing chamber, the O₂ gas is excited byplasma and is made to flow as active species. Accordingly, thetemperature of the wafer 200 can be set to a low temperature range setas described above. However, since the change in temperature takes time,it is preferable that the temperature of the wafer is set to be equal tothe temperature at the time of supplying the BTBAS gas.

At this time, the gas flowing in the processing chamber 201 is theactive species (O₂ plasma) obtained by exciting the O₂ gas by plasma andthe BTBAS gas is not made to flow in the processing chamber 201.Accordingly, the O₂ gas does not cause a gas-phase reaction and the O₂gas changed to active species or activated reacts with asilicon-containing layer as the first layer formed on the wafer 200 instep S204. Accordingly, the silicon-containing layer is oxidized and isdeformed into a second layer containing silicon (the first element) andnitrogen (the second element), that is, a silicon oxide layer (SiOlayer).

When the valve 513 is turned on to cause N₂ (inert gas) to flow from thecarrier gas supply pipe 510 connected to the middle of the gas supplypipe 310, it is possible to prevent O₂ from going around to theBTBAS-side nozzle 410 or the gas supply pipe 310. Since it is intendedto prevent O₂ from going around, the flow rate of N₂ (inert gas)controlled by the mass flow controller 512 may be small.

Removal of Residual Gas: Step S307

In step S307, the residual gas such as residual O₂ not reacting orremaining after the oxidation is removed from the processing chamber201. The valve 323 of the gas supply pipe 320 is turned off to stop thesupply of O₂ to the processing chamber 201, the valve 622 is turned onto cause O₂ to flow to the vent line 620, the valve 333 of the gassupply pipe 330 is turned off to stop the supply of O₂ to the processingchamber 201, and the valve 632 is turned on to cause O₂ to flow to thevent line 630. At this time, the APC valve 243 of the exhaust pipe 231is fully turned on and the processing chamber 201 is exhausted up to 20Pa or lower by the use of the vacuum pump 246 to remove the residual gassuch as residual O₂ remaining in the processing chamber 201 from theprocessing chamber 201. At this time, when inert gas such as N₂ issupplied to the processing chamber 201 from the gas supply pipes 320 and330 which are O₂ supply lines and the gas supply line 310, the effect ofremoving the residual gas such as residual O₂ is improved.

By setting steps S304 to S307 as one cycle and performing at least onecycle (step S308), the silicon oxide film 706 (see FIG. 30C) or thesilicon oxide film 723 (see FIG. 31B) with a predetermined thickness isformed on the wafer 200 by the use of the ALD method.

By setting steps S304 to S307 as one cycle and performing at least onecycle, the silicon oxide film 706 (see FIG. 30C) containing silicon (thefirst element) and oxygen (the second element) with a predeterminedthickness is formed as the first resist protecting film on the firstresist pattern 705 and the hard mask 702 and the silicon oxide film 723(see FIG. 31B) is formed on the first resist pattern 722.

When the film forming process of forming the silicon oxide film 706 orthe silicon oxide film 723 with the predetermined thickness isperformed, the processing chamber 201 is purged with inert gas byexhausting the processing chamber 201 while supplying inert gas such asN₂ to the processing chamber 201 (gas purging step: step S310). The gaspurging step is preferably carried out by repeatedly performing both thesupply of inert gas such as N₂ to the processing chamber 201 which isperformed by turning off the APC valve 243 and turning on the valves513, 523, and 533 after removing the residual gas and the vacuum suctionof the processing chamber 201 which is performed by turning off thevalves 513, 523, and 533 to stop the supply of the inert gas such as N₂to the processing chamber and turning on the APC valve 243.

Thereafter, the boat rotating mechanism 267 is stopped to stop therotation of the boat 217. Thereafter, the valves 513, 523, and 533 areturned on to replace the atmosphere of the processing chamber 201 withthe inert gas such as N₂ (replacement with inert gas) and to return thepressure in the processing chamber 201 to the normal pressure (return toatmospheric pressure: step S312). Thereafter, the sealing cap 219 iselevated down by the boat elevator 115 to open the lower end of thereaction tube 203 and the boat 217 is unloaded to the outside of theprocessing chamber 201 from the lower end of the reaction tube 203 inthe state in which the processed wafers 200 are held in the boat 217(unloading of boat: step S314). Thereafter, the lower end of thereaction tube 203 is closed with the furnace opening shutter 147.Thereafter, the vacuum pump 246 is stopped. Thereafter, the processedwafers 200 are taken out of the boat 217 (discharging of wafer: stepS316). Accordingly, a film forming process (batch process) is ended.

A modification of the ninth embodiment will be described below withreference to FIG. 34.

In the ninth embodiment, the first plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protecting pipe 452,the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are symmetric with the line passing through the centerof the wafers 200 (the center of the reaction tube 203), the exhausthole 230 is disposed in the line passing through the centers of thewafers 200 (the center of the reaction tube 203), the gas supply holes411 of the nozzle 410 are disposed in the line passing through thecenters of the wafers 200 (the center of the reaction tube 203), and thefirst plasma generating structure 429 and the second plasma generatingstructure 439 are disposed in the vicinity of the exhaust hole 230. Thismodification is different from the ninth embodiment, in that the firstplasma generating structure 429 and the second plasma generatingstructure 439 are disposed at the positions (different by 180°) opposedto each other with the wafers 200 interposed therebetween, are disposedsymmetric about the center of the wafer 200 and the center of thereaction tube 203, and the nozzle 410 is disposed between the exhausthole 230 and the second plasma generating structure 439, but is the sameas the ninth embodiment in the other points.

In this modification, the first plasma source constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided.Therefore, compared with the case in which only one plasma source isprovided, it is possible to lower the input power density per unitvolume of the RF power by distributing and supplying the RF power toplural plasma sources, and thus to reduce the number of particlesgenerated, thereby improving the adhesion. Further, since the RF powersupplied to the plasma sources can be reduced, the damage to the wafers200 or the films formed on the wafers 200 can be reduced. Even when theRF power supplied to the plasma sources is reduced, a sufficient amountof plasma to process a substrate can be generated by the two plasmasources, thereby lowering the processing temperature of the wafers 200.

Since the first plasma generating structure 429 constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the bufferchamber 423, and the gas supply holes 425 and the second plasmagenerating structure 439 constituted by the rod-like electrode 481, therod-like electrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the buffer chamber 433, and the gas supply holes435 are disposed at the positions (different by 180°) opposed to eachother with the wafers 200 interposed therebetween and are disposedsymmetric about the center of the wafer 200 and the center of thereaction tube 203, it is easy to supply plasma uniformly to the entiresurfaces of the wafers 200 from both plasma generating structures and itis thus possible to form a uniform film on the wafers 200.

Another modification of the ninth embodiment will be described belowwith reference to FIG. 35.

In the ninth embodiment, the first plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protecting pipe 452,the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are symmetric with respect to the line passing throughthe center of the wafers 200 (the center of the reaction tube 203) andthe gas supply holes 411 of the nozzle 410 are disposed in the linepassing through the centers of the wafers 200 (the center of thereaction tube 203). This modification is different from the ninthembodiment, in that the first plasma generating structure 429 and thesecond plasma generating structure 439 are disposed symmetric withrespect to the line passing through the centers of the wafers 200 (thecenter of the reaction tube 203) but the gas supply holes 411 of thenozzle 410 are not disposed in the line passing through the centers ofthe wafers 200 (the center of the reaction tube 203), but is the same asthe ninth embodiment in the other points.

In this modification, the first plasma source constituted by therod-like electrode 471, the rod-like electrode 472, the electrodeprotecting pipe 451, the electrode protective pipe 452, the matchingunit 271, and the RF power source 270 and the second plasma sourceconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the matching unit 271, and the RF power source 270 are provided.Therefore, compared with the case in which only one plasma source isprovided, it is possible to lower the input power density per unitvolume of the RF power by distributing and supplying the RF power toplural plasma sources, and thus to reduce the number of particlesgenerated, thereby improving the adhesion. Further, since the RF powersupplied to the plasma sources can be reduced, the damage to the wafers200 or the films formed on the wafers 200 can be reduced. Even when theRF power supplied to the plasma sources is reduced, a sufficient amountof plasma to process a substrate can be generated by the two plasmasources, thereby lowering the processing temperature of the wafers 200.

Since the first plasma generating structure constituted by the rod-likeelectrode 471, the rod-like electrode 472, the electrode protecting pipe451, the electrode protective pipe 452, the buffer chamber 423, and thegas supply holes 425 and the second plasma generating structureconstituted by the rod-like electrode 481, the rod-like electrode 482,the electrode protecting pipe 461, the electrode protective pipe 462,the buffer chamber 433, and the gas supply holes 435 are disposedsymmetric with respect to a line passing through the center of thewafers 200 (the center of the reaction tube 203), it is easy to supplyplasma uniformly to the entire surfaces of the wafers 200 from bothplasma generating structures and it is thus possible to form a uniformfilm on the wafers 200.

Still another modification of the embodiment will be described belowwith reference to FIG. 36.

In this modification, a third plasma generating structure 439′constituted by a rod-like electrode 481′, a rod-like electrode 482′, anelectrode protecting pipe 461′, an electrode protecting pipe 462′, abuffer chamber 433′, and a gas supply holes 435′ and having the samestructure as the second plasma generating structure 439 constituted bythe rod-like electrode 481, the rod-like electrode 482, the electrodeprotecting pipe 461, the electrode protecting pipe 462, the bufferchamber 433, and the gas supply holes 435 is added to the modificationshown in FIG. 35, and the third plasma generating structure 439′ and thefirst plasma generating structure 429 constituted by the rod-likeelectrode 471, the rod-like electrode 472, the electrode protecting pipe451, the electrode protecting pipe 452, the buffer chamber 423, and thegas supply holes 425 are disposed to be symmetric with respect to theline passing through the center of the wafers 200 and the center of thereaction tube 203.

In this modification, the third plasma source constituted by therod-like electrode 481′, the rod-like electrode 482′, the electrodeprotecting pipe 461′, the electrode protective pipe 462′, the matchingunit 271, and the RF power source 270 is added to the first plasmasource constituted by the rod-like electrode 471, the rod-like electrode472, the electrode protecting pipe 451, the electrode protective pipe452, the matching unit 271, and the RF power source 270 and the secondplasma source constituted by the rod-like electrode 481, the rod-likeelectrode 482, the electrode protecting pipe 461, the electrodeprotective pipe 462, the matching unit 271, and the RF power source 270.Therefore, compared with the case in which two plasma sources areprovided, it is possible to still lower the input power density per unitvolume of the RF power by distributing and supplying the RF power to thethree plasma sources, and thus to further reduce the number of particlesgenerated, thereby further improving the adhesion. Further, since the RFpower supplied to the plasma sources can be further reduced, the damageto the wafers 200 or the films formed on the wafers 200 can be furtherreduced. Even when the RF power supplied to the plasma sources isreduced, a sufficient amount of plasma to process a substrate can begenerated by the three plasma sources, thereby lowering the processingtemperature of the wafers 200.

Tenth Embodiment

A tenth embodiment of the invention will be described below withreference to FIGS. 37 and 38.

In the ninth embodiment, the electrode protecting pipe 461 and theelectrode protecting pipe 462 are inserted into the buffer chamber 423via the through-holes 204 and 205 formed in the reaction tube 203 at aheight position close to the lower part of the boat support 218, therod-like electrodes 481 and 482 are inserted into the buffer chamber 423at the height position close to the lower part of the boat support 218,the electrode protecting pipe 461 and the electrode protecting pipe 462are fixed to the buffer chamber 423 by the use of the attachment plate401, and the electrode protecting pipes 451 and 452 and the rod-likeelectrodes 471 and 472 are the same structures as the electrodeprotecting pipes 461 and 462 and the rod-like electrodes 481 and 482.This embodiment is different from the ninth embodiment, in that theelectrode protecting pipe 461 and the electrode protecting pipe 462 areinserted into the buffer chamber 423 via the through-holes 206 and 207formed in the reaction tube 203 at a position lower than the height ofthe upper part (a part slightly lower than the lowermost wafer of thestacked wafers) of the boat support 218 and are disposed outside thereaction tube 203 at a position lower than the height of the upper part(a part slightly lower than the lowermost wafer of the stacked wafers)of the boat support 218, the rod-like electrodes 481 and 482 areinserted into the buffer chamber 423 at the height position close to theupper part of the boat support 218 and are disposed outside the reactiontube 203 at a position lower than the height of the upper part (a partslightly lower than the lowermost wafer of the stacked wafers) of theboat support 218, the electrode protecting pipe 461 and the electrodeprotecting pipe 462 are disposed outside the reaction tube 203 to passthrough holes 405 and 406 of the attachment plate 401 and are fixed bythe attachment plate 401, the attachment plate 401 is fixed to thereaction tube 203, and the electrode protecting pipes 451 and 452 andthe rod-like electrodes 471 and 472 have the same structure as theelectrode protecting pipes 461 and 462 and the rod-like electrodes 481and 482, but is the same in the other points. In this embodiment, sincethe rod-like electrodes 481 and 482 are inserted into the buffer chamber423 at the height position close to the upper part of the boat support218 and are disposed outside the reaction tube 203 at the position lowerthan the height position of the upper part (a part slightly lower thanthe lowermost wafer of the stacked wafers) of the boat support 218, itis possible to prevent the discharge at the position lower than theheight position of the upper part (a part slightly lower than thelowermost wafer of the stacked wafers) of the boat support 218. Thecurvature of a curved portion 491 of the rod-like electrode 482 (481,471, and 472) is greater than the curvature of a curved portion 490.

Eleventh Embodiment

An eleventh embodiment of the invention will be described with referenceto FIGS. 39 and 40.

In the ninth embodiment, the thickness of the rod-like electrodes 471,472, 481, and 482 is constant regardless of the height. This embodimentis different from the ninth embodiment, in that the rod-like electrodes471, 472, 481, and 482 is thinner below the height position of the upperpart (a part slightly lower than the lowermost wafer of the stackedwafers) of the boat support 218 than above the upper part of the boatsupport 218, but is the same in the other points. By reducing thethickness of the rod-like electrodes 471, 472, 481, and 482, the energyis lowered and the discharge below the height position of the upper part(a part slightly lower than the lowermost wafer of the stacked wafers)of the boat support 218 than above the upper part of the boat support218 can be suppressed, thereby suppressing the energy consumption.

Twelfth Embodiment

A twelfth embodiment of the invention will be described below withreference to FIGS. 41 and 42.

In the ninth embodiment, the first plasma generating structure 429constituted by the rod-like electrode 471, the rod-like electrode 472,the electrode protecting pipe 451, the electrode protecting pipe 452,the buffer chamber 423, and the gas supply holes 425 and the secondplasma generating structure 439 constituted by the rod-like electrode481, the rod-like electrode 482, the electrode protecting pipe 461, theelectrode protecting pipe 462, the buffer chamber 433, and the gassupply holes 435 are disposed inside the reaction tube 203. Thisembodiment is different from the ninth embodiment, in that the plasmagenerating structures 820 and 830 are disposed to protrude to theoutside from the reaction tube 203, but is the same in the other points.Plasma-generating structures 820 and 830 have the same structure as theplasma-generating structures 820 and 830 of the sixth embodiment.

Remote plasma is generated by the plasma generating structures 820 and830 having the above-mentioned configuration. That is, radicalsgenerated in the plasma generating structures 820 and 830 are notdeactivated until reaching the entire surfaces of the wafers 200 in theprocessing chamber 201 and ions generated by the plasma generatingstructures 820 and 830 do not reach the wafers to such an extent todamage the wafers 200 in the processing chamber.

As in this embodiment, when the plasma generating structures 820 and 830are disposed to protrude to the outside of the reaction tube 203, thedistance between the outer peripheries of the wafers 200 and the innerperipheral surface of the reaction tube 203 can be reduced, comparedwith the case in which the buffer chambers 423 and 433 are disposedinside the reaction tube 203 as in the first embodiment.

In this embodiment, the first plasma source constituted by plasmagenerating electrodes 473 and 474, the matching unit 271, and the RFpower source 270 and the second plasma source constituted by the plasmagenerating electrodes 483 and 484, the matching unit 271, and the RFpower source 270 are provided. Therefore, compared with the case inwhich only one plasma source is provided, even when the RF powersupplied to the each plasma source is reduced, a sufficient amount ofplasma to process a substrate can be generated by the two plasmasources, thereby the damage to the wafers 200 or the films formed on thewafers 200 can be reduced, and the processing temperature of the wafers200 can be lowered.

Since the first plasma generating structure 820 constituted by theplasma generating electrodes 473 and 474, the plasma generating chamberwall 428, the plasma generating chamber 821, the opening 822, the nozzle426, and the gas supply holes 427 and the second plasma generatingstructure 830 constituted by the plasma generating electrodes 483 and484, the plasma generating chamber wall 438, the plasma generatingchamber 831, the opening 832, the nozzle 436, and the gas supply holes437 are disposed symmetric with respect to a line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200from both plasma generating structures and it is thus possible to form auniform film on the wafers 200.

Since the exhaust hole 230 is disposed on the line passing through thecenter of the wafers 200 (the center of the reaction tube 203), it iseasy to supply plasma uniformly to the entire surfaces of the wafers 200and it is thus possible to form a uniform film on the wafers 200. Sincethe gas supply holes 411 of the nozzle 410 are also disposed on the linepassing through the center of the wafers 200 (the center of the reactiontube 203), it is easy to supply plasma uniformly to the entire surfacesof the wafers 200 and it is thus possible to form a uniform film on thewafers 200.

In the ninth to twelfth embodiments, the vaporizer 315 is used tovaporize a liquid raw material, but a bubbler may be used instead of thevaporizer.

In the above-mentioned exemplary embodiments, an example using the ALDmethod has been described. However, in a case in which the CVD method isused, the RF power can be distributed by providing plural plasma sourcesand a sufficient amount of plasma can be generated even when the RFpower supplied to the plasma sources is lower than that in the case ofone plasma source. Accordingly, it is possible to reduce the damage tothe wafers 200 or the film to be formed when processing the wafers 200by plasma and to lower the processing temperature of the wafers 200. Itis possible to suppress the generation of particles.

In the above-mentioned exemplary embodiments, a CCP (CapacitivelyCoupled Plasma) type RF power source is used. However, even when an ICP(Inductively Coupled Plasma) type RF power source is used, the sameadvantages can be achieved.

In the above-mentioned exemplary embodiments, N₂ (nitrogen) is used asthe carrier gas, but He (helium), Ne (neon), Ar (argon), and the likemay be used instead of nitrogen.

Preferred Aspects of the Embodiments

Hereinafter, preferred aspects of the embodiments will be additionallydescribed.

APPENDIX 1

According to an aspect of the preferred embodiments, there is provided asubstrate processing apparatus including:

a processing chamber in which a substrate is processed;

one or more buffer chambers that are partitioned from the processingchamber and that includes a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the processing chamber;

a second processing gas supply system that supplies a second processinggas to the one or more buffer chambers;

a power source that outputs RF power;

a plasma-generating electrode that activates the second processing gasin the one or more buffer chambers with an application of the RF powerfrom the power source; and

a controller that controls the first processing gas supply system, thepower source, and the second processing gas supply system to expose thesubstrate having a metal film formed on a surface thereof to the firstprocessing gas and the second processing gas to form a first film on themetal film in a state in which the RF power is not applied to theelectrode and thereafter to expose the substrate having the first filmformed thereon to the first processing gas, and the second processinggas that is activated with the application of the RF power to theelectrode to form a second film on the metal film.

APPENDIX 2

According to another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

a processing chamber in which a substrate is processed;

one or more buffer chambers that are partitioned from the processingchamber and that includes a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the processing chamber;

a second processing gas supply system that supplies a second processinggas to the one or more buffer chambers;

a power source that outputs RF power;

a plasma-generating electrode that activates the second processing gasin the one or more buffer chambers with an application of the RF powerfrom the power source; and

a controller that controls the first processing gas supply system, thepower source, and the second processing gas supply system to expose thesubstrate having a metal film formed on a surface thereof to the firstprocessing gas and thereafter to expose the substrate to the firstprocessing gas, and the second processing gas that is activated with theapplication of the RF power to the electrode to form a film on the metalfilm.

APPENDIX 3

In the substrate processing apparatus according to the appendix 1 or 2,preferably, the substrate processing apparatus further includes anexhaust system that exhausts the processing chamber, and the controlleris the controller that controls the first processing gas supply system,the power source, and the second processing gas supply system toalternately supply the first processing gas and the activated secondprocessing gas to the processing chamber so as not to be mixed with eachother and to form the film on the metal film.

APPENDIX 4

In the substrate processing apparatus according to any one of theappendices 1 to 3, preferably, the metal film is a GST film.

APPENDIX 5

In the substrate processing apparatus according to the appendix 4,preferably, the first processing gas is DCS and the second processinggas is NH₃.

APPENDIX 6

In the substrate processing apparatus according to any one of theappendices 1 to 5, preferably, the substrate processing apparatusincludes plural buffer chambers.

APPENDIX 7

In the substrate processing apparatus according to the appendix 5,preferably, the substrate processing apparatus further includes aheating system that heats the substrate, and

the control means controls the first processing gas supply system, thepower source, the second processing gas supply system, and the heatingsystem to heat the substrate having the metal film formed on the surfacethereof to a self-decomposition temperature of the DCS or lower and toexpose the substrate to the first processing gas and then to heat thesubstrate to the self-decomposition temperature of the DCS or lower andto expose the substrate to the first processing gas, and the secondprocessing gas that is activated with the application of the RF power tothe electrode to form the film on the metal film.

APPENDIX 8

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method including:

loading a substrate having a metal film formed on a surface thereof intoa processing chamber;

supplying a first processing gas, and a second processing gas that isnot activated by plasma excitation to the processing chamber from pluralprocessing gas supply systems independent of each other to pre-processthe substrate;

supplying the first processing gas, and the second processing gas thatis activated by the plasma excitation to the processing chamber from theplural processing gas supply systems to form a predetermined film on thepre-processed substrate; and

unloading the substrate having the predetermined film formed thereonfrom the processing chamber.

APPENDIX 9

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method including:

loading a substrate having a metal film formed on a surface thereof intoa processing chamber;

supplying a first processing to the processing chamber from pluralprocessing gas supply systems independent of each other to pre-processthe substrate;

supplying the first processing gas, and the second processing gas thatis activated by plasma excitation to the processing chamber from theplural processing gas supply systems to form a predetermined film on thepre-processed substrate; and

unloading the substrate having the predetermined film formed thereonfrom the processing chamber.

APPENDIX 10

In the semiconductor device manufacturing method according to theappendix 8 or 9, preferably, the predetermined film forming is performedby alternately supplying the first processing gas and the activatedsecond processing gas to the processing chamber from the pluralprocessing gas supply systems so as not to be mixed with each other toform the predetermined film on the pre-processed substrate.

APPENDIX 11

In the semiconductor device manufacturing method according to any one ofthe appendices 8 to 10, preferably, the metal film is a GST film.

APPENDIX 12

In the semiconductor device manufacturing method according to theappendix 11, preferably, the first processing gas is DCS and the secondprocessing gas is NH₃.

APPENDIX 13

In the semiconductor device manufacturing method according to theappendix 12, preferably, the substrate is heated to a self-decompositiontemperature of the first processing gas or lower to pre-process thesubstrate and to form the predetermined film on the pre-processedsubstrate.

APPENDIX 14

According to still another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

a processing chamber in which a substrate is processed;

plural buffer chambers that are partitioned from the processing chamberand that respectively include a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the processing chamber;

a second processing gas supply system that supplies a second processinggas to the plural buffer chambers;

a power source that outputs RF power;

plasma-generating electrodes that activate the second processing gas ineach of the buffer chambers with an application of the RF power from thepower source;

a heating system that heats the substrate; and

a controller that controls the first processing gas supply system, thepower source, the second processing gas supply system, and the heatingsystem to expose the substrate having a metal film formed on a surfacethereof to the first processing gas, and the second processing gas thatis activated in the plural buffer chambers with an application of RFpower to the electrodes and that is supplied from the plural bufferchambers to the processing chamber to form a film on the metal filmwhile heating the substrate to a self-decomposition temperature of thefirst processing gas or lower.

APPENDIX 15

In the substrate processing apparatus according to the appendix 14,preferably, the controller is the controller that controls the firstprocessing gas supply system, the power source, the second processinggas supply system, and the heating system to alternately supply thefirst processing gas and the activated second processing gas to theprocessing chamber so as not to be mixed with each other and to form thefilm on the metal film.

APPENDIX 16

In the substrate processing apparatus according to the appendix 15,preferably, the substrate processing apparatus further includes anexhaust system that exhausts the processing chamber, and the controlleris the controller that controls the first processing gas supply system,the power source, and the second processing gas supply system, theheating system, and the exhaust system to alternately supply the firstprocessing gas and the activated second processing gas to the processingchamber so as not to be mixed with each other and to form the film onthe metal film.

APPENDIX 17

In the substrate processing apparatus according to any one of theappendices 13 to 15, preferably, the metal film is a GST film.

APPENDIX 18

In the substrate processing apparatus according to the appendix 16,preferably, the first processing gas is DCS and the second processinggas is NH_(3.)

APPENDIX 19

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method including:

loading a substrate having a metal film formed on a surface thereof intoa processing chamber;

exposing the substrate having the metal film formed on the surfacethereof to a first processing gas, and a second processing gas which isactivated by plural plasma generating structures and supplied to theprocessing chamber from the plural plasma generating structures andforming a film on the metal film while heating the substrate to aself-decomposition temperature of the first processing gas or lower; and

unloading the substrate having the film formed thereon form theprocessing chamber.

APPENDIX 20

In the substrate processing apparatus according to the appendix 19,preferably, the metal film is a GST film.

APPENDIX 21

In the substrate processing apparatus according to the appendix 20,preferably, the first processing gas is DCS and the second processinggas is NH_(3.)

APPENDIX 22

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufactured using the semiconductordevice manufacturing method according to any one of the appendices 8 to13 and 19 to 21.

APPENDIX 23

According to a still another aspect of the preferred embodiments, thereis provided a program that causes computer to perform a processincluding:

controlling plural processing gas supply systems independent of eachother and plasma activation unit to supply a first processing gas, and asecond processing gas that is not activated by plasma excitation to aprocessing chamber from the plural processing gas supply systems topre-process a substrate, and thereafter to supply the first processinggas, and the second processing gas that is activated by the plasmaexcitation to the processing chamber from the plural processing gassupply systems to form a predetermined film on the pre-processedsubstrate.

APPENDIX 24

According to a still another aspect of the preferred embodiments, thereis provided a program that causes computer to perform a processincluding:

controlling plural processing gas supply systems independent of eachother and plasma activation unit to supply a first processing to theprocessing chamber to pre-process a substrate, and thereafter to supplythe first processing gas, and the second processing gas that isactivated by plasma excitation to the processing chamber from the pluralprocessing gas supply systems to form a predetermined film on thepre-processed substrate.

APPENDIX 25

According to a still another aspect of the preferred embodiments, thereis provided a program that causes computer to perform a processincluding:

controlling plural processing gas supply systems independent of eachother, heating system to heat a substrate, and plural plasma generatingstructures to expose the substrate having a metal film formed on asurface thereof to a first processing gas, and a second processing gasthat is activated by the plural plasma generating structures andsupplied to the processing chamber from the plural plasma generatingstructures and to form a film on the metal film while heating thesubstrate to a self-decomposition temperature of the first processinggas or lower.

APPENDIX 26

According to a still another aspect of the preferred embodiments, thereis provided a non-transitory computer-readable medium storing theprogram according to any one of the appendices 23 to 25,

APPENDIX 27

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus including thenon-transitory computer-readable medium according to the appendix 26.

APPENDIX 28

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus that forms an amorphoussilicon nitride film on a metal film with a high adhesion at atemperature of 350° C. or lower by reducing a supply power density perunit area of RF power to be supplied.

APPENDIX 29

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus that forms an amorphoussilicon nitride film on a metal film with a high adhesion at atemperature of 350° C. or lower in a processing chamber including two ormore buffer chambers to be supplied with RF power by distributing andsupplying the RF power to be supplied to the two or more bufferchambers.

APPENDIX 30

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus that forms an amorphoussilicon nitride film on a metal film with a high adhesion by repeatedlyperforming a DCS application and an NH₃ application without a supply ofRF power one or more times and then repeatedly performing the DCSapplication and the NH₃ application with the supply of RF power one ormore times.

APPENDIX 31

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus that forms an amorphoussilicon nitride film on a metal film with a high adhesion by performinga DCS application and then repeatedly performing the DCS application andthe NH₃ application with the supply of RF power one or more times.

APPENDIX 32

According to still another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

a processing chamber in which a substrate is processed;

plural buffer chambers that are partitioned from the processing chamberand that respectively include a gas supply hole opened to the processingchamber;

a first processing gas supply system that supplies a first processinggas to the plural buffer chambers;

a power source that outputs RF power;

plasma-generating electrodes that activate the first processing gas ineach of the buffer chambers with an application of the RF power from thepower source;

a second processing gas supply system that supplies a second processinggas to the processing chamber;

an exhaust system that exhausts the processing chamber;

a heating system that heats the substrate; and

a controller that controls the first processing gas supply system, thepower source, the second processing gas supply system, the exhaustsystem and the heating system to expose the substrate to the activatedfirst processing gas and the second processing gas to form a film on thesubstrate while heating the substrate to 200° C. or lower.

APPENDIX 33

In the substrate processing apparatus according to the appendix 32,preferably, the processing chamber and the buffer chambers are disposedin a reaction tube.

APPENDIX 34

In the substrate processing apparatus according to the appendix 32 or33, preferably, the electrodes are disposed inside the buffer chambers.

APPENDIX 35

In the substrate processing apparatus according to the appendix 32 or33, preferably, the electrodes are disposed outside the buffer chambers.

APPENDIX 36

In the substrate processing apparatus according to any one of theappendices 32 to 35, preferably, the second processing gas is usedwithout being activated.

APPENDIX 37

In the substrate processing apparatus according to the appendix 32,preferably, the first processing gas is an oxygen-containing gas, thesecond processing gas is a silicon-containing gas, and the film formedon the substrate is a silicon oxide film.

APPENDIX 38

In the substrate processing apparatus according to the appendix 37,preferably, the first processing gas is oxygen and the second processinggas is BTBAS.

APPENDIX 39

In the substrate processing apparatus according to the appendix 32,preferably, the film is formed while heating the substrate to 100° C. orlower.

APPENDIX 40

In the substrate processing apparatus according to the appendix 32,preferably, the second processing gas supply system is connected to anozzle with a gas supply hole disposed upright in the processing chamberand supplies the second processing gas to the processing chamber fromthe gas supply hole via the nozzle,

the exhaust system may be connected to an exhaust hole opened to theprocessing chamber, and

the gas supply hole of the nozzle and the exhaust hole may be disposedat positions opposed to each other with the substrate interposedtherebetween.

APPENDIX 41

In the substrate processing apparatus according to the appendix 40,preferably, the plural buffer chambers are disposed so that distancesbetween gas supply holes of the plural buffer chambers and the gassupply hole of the nozzles are substantially the same.

APPENDIX 42

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method of forming asilicon oxide film on a substrate having a pattern of resist oramorphous carbon formed thereon by performing, while heating thesubstrate to 200° C. or lower,

exposing the substrate to a first processing gas which is activated byplasma generated in plural buffer chambers with an application of RFpower to an electrode; and

exposing the substrate to a second processing gas which is not activatedby plasma.

APPENDIX 43

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufactured by the semiconductor devicemanufacturing method according to the appendix 42.

APPENDIX 44

According to still another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

two or more plasma-generating buffer chambers that are disposed in aprocessing chamber;

RF power supply means that distributes and supplies RF power to the twoor more plasma-generating buffer chambers.

APPENDIX 45

In the substrate processing apparatus according to the appendix 44,preferably, the substrate processing apparatus is provided with ahigh-frequency electrode having a structure in which the thickness atthe lower end of the processing chamber decreases.

APPENDIX 46

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method including:

supplying a first raw material containing silicon to plural substrates;

exhausting the first raw material and a byproduct gas thereof for apredetermined time;

generating plasma while supplying ammonia to a plasma-generating bufferchamber and supplying ammonia radical to the plural substrates; and

exhausting the residual gas for a predetermined time.

APPENDIX 47

According to still another aspect of the preferred embodiments, there isprovided a semiconductor device manufacturing method including:

supplying a first raw material containing silicon to plural substrates;

exhausting the first raw material and a byproduct gas thereof for apredetermined time;

generating plasma while supplying oxygen to a plasma-generating bufferchamber and supplying oxygen radical to the plural substrates; and

exhausting the residual gas for a predetermined time.

APPENDIX 48

According to still another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

a processing chamber in which a substrate is processed;

a heating unit that heats the processing chamber;

plural plasma generating chambers that are partitioned from theprocessing chamber and that each have a gas supply hole opened to theprocessing chamber;

a first source gas supply system that supplies a first source gas to theplural plasma-generating chambers;

a RF power source that outputs RF power;

plural plasma-generating electrodes that excite the first source gas inthe plural plasma-generating chambers by applying the RF power from theRF power source;

a second source gas supply system that supplies a second source gas tothe processing chamber;

an exhaust system that exhausts the processing chamber; and

a controller that controls the heating unit, the first source gas supplysystem, the RF power source, the second source gas supply system and theexhaust system to expose the substrate to the activated first processinggas and the second processing gas to form a film on the substrate whileheating the substrate to 200° C. or lower.

APPENDIX 49

According to still another aspect of the preferred embodiments, there isprovided a substrate processing apparatus including:

a processing chamber in which a substrate is processed;

a heating unit that heats the processing chamber;

a temperature detecting unit that detects the temperature of theprocessing chamber;

plural plasma generating chambers that are partitioned from theprocessing chamber and that each have a gas supply hole opened to theprocessing chamber;

a first source gas supply system that supplies a first source gas to theplural plasma-generating chambers and that includes first flow ratecontrol means controlling the flow rate of the first source gas and afirst valve controlling the supply of the first source gas to the pluralplasma-generating chambers;

a RF power source that outputs RF power;

plural plasma-generating electrodes that excite the first source gas inthe plural plasma-generating chambers by applying the RF power from theRF power source;

a second source gas supply system that supplies a second source gas tothe processing chamber and that includes second flow rate control meanscontrolling the flow rate of the second source gas and a second valvecontrolling the supply of the second source gas to the processingchamber;

an exhaust system that exhausts the processing chamber; and

a controller that controls the heating unit to heat the processingchamber to 200° C. or lower on the basis of temperature informationdetected by the temperature detecting unit, controls the RF power sourceto apply predetermined RF power to the plural electrodes, controls thefirst flow rate control unit and the first valve to supply the firstsource gas to the plural plasma-generating chambers by predeterminedamounts, respectively, controls the second flow rate control unit andthe second valve to supply the second source gas to the processingchamber by a predetermined amount, and controls the exhaust system toexhaust the processing chamber with a predetermined displacement.

APPENDIX 50

According to another exemplary aspect of the invention, there isprovided a semiconductor device manufacturing method including:

controlling heating means for heating a processing chamber, in which asubstrate is processed, to heat the processing chamber to a temperatureof 200° C. or lower on the basis of temperature information detected bytemperature detecting means for detecting the temperature of theprocessing chamber;

controlling a first source gas supply system, which supplies a firstsource gas to plural plasma-generating chambers being partitioned fromthe processing chamber and each having a gas supply hole opened to theprocessing chamber, to supply the first source gas to the pluralplasma-generating chambers by predetermined amounts, respectively;

controlling a RF power source, which outputs RF power, to apply apredetermined amount of RF power to plural plasma-generating electrodesexciting the first source gas in the plural plasma-generating chambers,respectively, by applying the RF power from the RF power source;

controlling a second source gas supply system, which supplies a secondsource gas to the processing chamber, to supply the second source gas tothe processing chamber by a predetermined amount;

controlling an exhaust system, which exhausts the processing chamber, toexhaust the processing chamber with a predetermined displacement; and

exposing the substrate to the activated first source gas and the secondsource gas while heating the substrate to a temperature of 200° C. orlower to form a film on the substrate.

APPENDIX 51

According to a still another aspect of the preferred embodiments, thereis provided a program that causes computer to perform a processincluding:

controlling heating means for heating a processing chamber, in which asubstrate is processed, to heat the processing chamber to a temperatureof 200° C. or lower on the basis of temperature information detected bytemperature detecting means for detecting the temperature of theprocessing chamber;

controlling a first source gas supply system, which supplies a firstsource gas to plural plasma-generating chambers being partitioned fromthe processing chamber and each having a gas supply hole opened to theprocessing chamber, to supply the first source gas to the pluralplasma-generating chambers by predetermined amounts, respectively;

controlling a RF power source, which outputs RF power, to apply apredetermined amount of RF power to plural plasma-generating electrodesexciting the first source gas in the plural plasma-generating chambers,respectively, by applying the RF power from the RF power source;

controlling a second source gas supply system, which supplies a secondsource gas to the processing chamber, to supply the second source gas tothe processing chamber by a predetermined amount; and

controlling an exhaust system, which exhausts the processing chamber, toexhaust the processing chamber with a predetermined displacement.

APPENDIX 52

According to a still another aspect of the preferred embodiments, thereis provided a non-transitory computer-readable medium storing theprogram according to the appendix 51.

APPENDIX 53

According to a still another aspect of the preferred embodiments, thereis provided a substrate processing apparatus including thenon-transitory computer-readable medium according to the appendix 52.

Various exemplary embodiments of the invention have hitherto beendescribed, however, the invention is not limited to the exemplaryembodiments. Therefore, the scope of the invention is limited only bythe appended claims.

What is claimed is:
 1. A method of manufacturing a semiconductor devicecomprising: performing a pre-process to a metal film or a GST film bysupplying a first processing gas to a substrate, on a surface of whichthe metal film or the GST film is formed, without supplying a secondprocessing gas; and performing a formation process to the substrate towhich the pre-process has been performed such that a film is formed onthe metal film or the GST film by executing at least one cycle ofalternately (i) supplying the first processing gas, and (ii) supplyingthe second processing gas that is activated by plasma excitation.
 2. Themethod according to claim 1, wherein, in the pre-process and theformation process, the substrate is heated to a temperature that isequal to or less than a self-decomposition temperature of the firstprocessing gas.
 3. The method according to claim 1, wherein the metalfilm comprises at least one selected from a group consisting of Ti, TiN,TiSi, W, WN, WSi, Co, CoSi, Al, AlSi, Cu, or alloys thereof.
 4. Asubstrate processing apparatus comprising: a processing chamber in whicha substrate is processed; at least one buffer chamber that ispartitioned from the processing chamber and that includes a gas supplyhole opened to the processing chamber; a first processing gas supplysystem configured to supply a first processing gas into the processingchamber; a second processing gas supply system configured to supply asecond processing gas into the processing chamber via the bufferchamber; a plasma source configured to generate plasma in the bufferchamber and activate the second processing gas by plasma excitation inthe buffer chamber; and a controller configured to control the firstprocessing gas supply system, the second processing gas supply system,and the plasma source such that (A) a pre-process is performed to ametal film or a GST film by supplying a first processing gas to asubstrate, on a surface of which the metal film or the GST film isformed, without supplying a second processing gas, and (B) a formationprocess is performed to the substrate to which the pre-process has beenperformed so as to form a film on the metal film or the GST film byexecuting at least one cycle of alternately (i) supplying the firstprocessing gas, and (ii) supplying the second processing gas that isactivated by plasma excitation.
 5. A non-transitory computer readablestorage medium storing a program that causes a computer to perform aprocess, the process comprising: performing a pre-process to a metalfilm or a GST film by supplying a first processing gas to a substrate,on a surface of which the metal film or the GST film is formed, withoutsupplying a second processing gas; and performing a formation process tothe substrate to which the pre-process has been performed such that afilm is formed on the metal film or the GST film by executing at leastone cycle of alternately (i) supplying the first processing gas, and(ii) supplying the second processing gas that is activated by plasmaexcitation.